Foam compositions and uses thereof

ABSTRACT

Components for articles of footwear and athletic equipment including a foam are provided. The foam portion of the components and articles include a composition which includes a thermoplastic copolyester, the composition having a foam structure. A polymer layer is provided on at least on surface of the foam portion. The polymer layer can control or reduce the water uptake of the foam portion. Methods of making the compositions, foams, and components are provided, as well as methods of making an article of footwear including one of the foam components. In some aspects, the foams and foam components can be made by injection molding, or injection molding followed by compression molding.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to, and the benefit of, co-pending U.S.provisional applications entitled “FOAM COMPOSITIONS AND USES THEREOF”having serial nos. 62/899,688, 62/899,696, and 62/899,742, each filed onSep. 12, 2019, the contents of which are incorporated by reference intheir entireties.

TECHNICAL FIELD

The present disclosure generally relates to foams formed ofthermoplastic copolyesters, and in particular to foams formed ofthermoplastic copolyesters which are suitable for the footwear andrelated industries and uses thereof.

BACKGROUND

The design of athletic equipment and apparel as well as footwearinvolves a variety of factors from the aesthetic aspects, to the comfortand feel, to the performance and durability. While design and fashionmay be rapidly changing, the demand for increasing performance in themarket is unchanging. To balance these demands, designers employ avariety of materials and designs for the various components that make upathletic equipment and apparel as well as footwear.

BRIEF DESCRIPTION OF THE DRAWINGS

Further aspects of the present disclosure will be readily appreciatedupon review of the detailed description, described below, when taken inconjunction with the accompanying drawings.

FIG. 1 is an elevation view of an article of footwear with a solecomponent according to an aspect of the invention.

FIG. 2 is an exploded view of the sole component of the article offootwear of FIG. 1.

FIG. 3 is a plan view of the bottom of the sole component of the articleof footwear of FIG.

FIG. 4 is a bottom view of an insert for use in a sole component of anarticle of footwear.

FIG. 5 is a top view of the insert of FIG. 4 inserted in a first portionto form a sole component.

FIG. 6 shows representative compression data for representative foamplaques comprising a disclosed composition and prepared using adisclosed method.

FIG. 7 shows a representative schematic illustrating a disclosed foamcomponent or article with a second polymeric material.

FIG. 8 shows a representative schematic illustrating a disclosed methodfor determining peak and tail temperatures.

FIGS. 9A-9D show representative images of cross-sectional views of foamplaques prepared using a disclosed thermoplastic copolyester elastomerat different temperatures. Each image shows a scalar bar (500micrometers). Foamed plaques were prepared at the followingtemperatures: 175 degrees C. (FIG. 9A); 190 degrees C. (FIG. 9B); 205degrees C. (FIG. 9C); and 245 degrees C. (FIG. 9D).

FIG. 10 shows a representative image of a cross-sectional view of a foamplaque prepared using a disclosed thermoplastic copolyester elastomer160 degrees C. The image shows a scalar bar (500 micrometers).

FIG. 11 shows representative coefficient of friction on a wood surfacedata for various polymeric materials.

FIG. 12 shows representative coefficient of friction on a concretesurface data for various polymeric materials.

FIG. 13 shows representative coefficient of friction on a concretesurface data for various polymeric materials used in a blown outsole.

FIG. 14 shows representative specific gravity data for various polymericmaterials in unfoamed samples and various foamed samples.

FIGS. 15A-15B show representative cross-sectional top plan views for amold with an injection cavity have a four-gate configuration (FIG. 15A)or a six-gate configuration (FIG. 15B).

FIGS. 16A-16I shown representative images for molded components preparedusing a four-gate configuration or a six-gate configuration. FIGS.16A-16C show photographic images of foam cross-sections obtained fromthe regions identified respectively as A, B, and C in the image for acomponent injection molded with the four-gate configuration shown inFIG. 16G. and FIGS. 16D-16F show photographic images of foamcross-sections obtained from the regions identified respectively as D,E, and F in the image for a component injection molded with thefour-gate configuration shown in FIG. 16H. FIG. 16I shows arepresentative defect free foam microstructure characteristic of eithergating scenario.

DETAILED DESCRIPTION

The present disclosure is directed to a foam article which includes afirst component, i.e., a foam component comprising a foamedthermoplastic copolyester composition, and a second component comprisinga second polymeric composition. The disclosed foam article includes thesecond component disposed on at least a portion of the first component.The first component is a foam component that includes a foamedthermoplastic copolyester composition having a microcellular open-cellor closed-cell foam structure. The second component has a secondpolymeric composition that includes a second polymeric material whichcan one or more thermoplastic copolyesters, or a polymeric material thatcan be substantially free of thermoplastic copolyesters. The secondpolymeric composition can comprise a thermoplastic elastomer orthermoplastic vulcanizate material. of the first component of the foamarticle can be a midsole or a midsole component. The second component ofthe foam article can be a ground contacting component such as an outsoleor a rand on an article of footwear, a reinforcing skin or a containmentlayer on a cushioning element, or other application.

Conventionally, vulcanized and peroxide-cured natural and syntheticrubbers such as isoprene and polybutadiene rubbers have been used toform durable, abrasion-resistant outer protective layers for a widevariety of articles, including outsoles for articles of footwear. Rubberformulations used for outsoles also typically provide traction. Onedisadvantage of using conventional rubber materials is that thesematerials are highly crosslinked during the curing process, renderingthe cured rubber a thermoset material and making it difficult to recycleor reuse the cured rubber. Also, it can be difficult to bond othermaterials to the cured rubber. Both the rubber materials and foammaterials typically used in a wide variety of consumer good are highlycrosslinked materials, which are formed and cured separately and thenadhered to each other using an adhesive system. These adhesive systemsrequire several manually-intensive processing steps, such as cleaningthe surfaces, priming the surfaces, applying adhesive to the surfaces,and pressing the surfaces together to bond them.

It has been found that thermoplastic copolyester compositions (i.e.,polymeric compositions comprising one or more thermoplastic copolyester)can be used to form microcellular foams having advantageous propertiesfor use in consumer article such as cushioning elements. When foamed asdescribed herein, these foams retain thermoplastic properties, making itpossible to readily recycle and reuse the foams. Additionally, it hasbeen found that these foams can be directly molded and foamed onto otherpolymeric materials (i.e., onto second polymeric materials as describedherein), which bonds the foam securely to the second polymeric materialwithout the need for additional adhesives, or the manual process stepsof applying an adhesive system. The second polymeric material which isbonded to the thermoplastic copolyester-based foam is a thermoplasticelastomeric material, such as a second thermoplastic copolyestercomposition or a thermoplastic vulcanizate material as described herein.Examples of both second thermoplastic copolyester compositions andthermoplastic vulcanizate materials which, when used either in solidform or in a lightly foamed form (e.g., having a specific gravity of0.85 or greater) have been found which both bond well to thethermoplastic copolyester-based foam during a molding and foamingprocess, and which also provide high levels of abrasion resistance andtraction under wet and dry conditions. When the second polymericmaterial is a second thermoplastic copolyester material, the fact thatthe foam comprises a first thermoplastic copolyester composition andthat the protective layer comprises a second thermoplastic copolyestercompositions provides the advantage that the entire article can easilybe melted down and combined material can be recycled. In this scenario,the second copolyester composition can each individually include one ormore of the same individual copolyesters present in the firstthermoplastic copolyester composition, either in the same proportions orin different proportions. Alternatively, the first and secondcopolyester compositions can each individually comprise differentcopolyesters.

The foam components disclosed herein are formed by foaming polymericcompositions comprising one or more thermoplastic copolyester into amicrocellular foam having an open-cell or closed-cell foam structure.Examples of thermoplastic copolyesters include polymers which have oneor more carboxylic acid moiety present in the polymeric backbone, on oneor more side chains, or both in the polymeric backbone and on one ormore side chains. The one or more carboxylic acid moiety of thethermoplastic copolyester can include a free carboxylic acid, a salt ofa carboxylic acid, or an anhydride of a carboxylic acid. In particularexamples, the carboxylic acid moiety can be an acrylic acid moiety or amethacrylic acid moiety. The foam articles comprising a microcellularopen-cell or closed-cell thermoplastic copolyester foam and a polymericlayer of the present disclosure are suitable for use in a variety ofarticles including for athletic equipment and apparel, particularlyfootwear (e.g., athletic footwear midsoles/outsoles). As discussedbelow, the microcellular open-cell or closed-cell thermoplasticcopolyester foam exhibits a unique balance of properties such as highenergy efficiency or energy return, high split tear, low specificgravity, and low compression set. The presence of the layer on at leasta portion of the exterior surface of the foam reduces liquid uptake bythe microcellular foams, particularly microcellular open-cell foams,increasing their performance when used under conditions where the foamcome into contact with liquids. Furthermore, the thermoplasticcopolyester foam can also be reprocessed with minimal loss in physicalproperties (e.g., for recycling), providing a solution for materialssustainability.

The second polymeric material of the polymeric layer can be selected toallow the entire foam article to be recycled in a single step, withoutthe need to remove or separate the polymeric layer from the foam. Forexample, the second polymeric material can comprise one or morethermoplastic copolyesters.

The foam article or foam component comprising the thermoplasticcopolyester foam can be formed by injection molding and foaming thethermoplastic copolyester polymeric material as described herein, or byinjection molding and foaming the thermoplastic copolyester polymericmaterial as described herein into a foam pre-form and subsequentlycompression molding the foam-preform into a finished foam. The secondpolymeric material can be disposed onto an exterior surface of the foamcomponent during an injection molding and foaming process, in which thefirst thermoplastic material is injected into a mold which includes thesecond polymeric material, and the second polymeric material bonds tothe foam during the molding process. Alternatively or additionally, thesecond polymeric material can be disposed onto the exterior surface ofthe foam component during a compression molding step, in which the foamcomponent is compression molded in a mold which includes the secondpolymeric material, and the second polymeric material bonds to the foamduring the molding process. Alternatively or additionally, the secondpolymeric material can be disposed onto the foam component after thefoam component has been formed, such as, for example.

Articles Manufactured Using the Disclosed Foams.

Footwear 10 is an exemplary article of athletic footwear that includesthe thermoplastic copolyester foam of the present disclosure. Whileillustrated as a running shoe, footwear 10 may alternatively beconfigured for any suitable athletic performance, such as baseballshoes, basketball shoes, soccer/global football shoes, American footballshoes, running shoes, cross-trainer shoes, cheerleading shoes, golfshoes, and the like. While an athletic shoe is exemplified in FIG. 1, itwill be readily understood that some of the terminology employed willalso apply to other articles of footwear or to other styles of shoe.Footwear 10 includes an upper 12 and a sole component 14 secured toupper 12. Sole component 14 can be secured to upper 12 by adhesive orany other suitable means. As used herein, the sole component 14 can be amonolithic component formed entirely of the thermoplastic copolyesterfoam material as described herein, or a multi-component assembly formedof a plurality of monolithic components, where at least one of themonolithic components is formed entirely of the thermoplasticcopolyester foam material as described herein.

Footwear 10 has a medial, or inner, side 16 and a lateral, or outer,side 18. For ease of discussion, footwear 10 can be divided into threeportions: a forefoot portion 20, a midfoot portion 22, and a heelportion 24. Portions 20, 22, and 24 are not intended to demarcateprecise areas of footwear 10. Rather, portions 20, 22, and 24 areintended to represent respective areas of footwear 10 that provide aframe of reference during the following discussion. Unless indicatedotherwise, directional terms used herein, such as rearwardly, forwardly,top, bottom, inwardly, downwardly, upwardly, etc., refer to directionsrelative to footwear 10 itself. Footwear 10 is shown in FIG. 1 in asubstantially horizontal orientation, as it would be positioned on ahorizontal surface when worn by a wearer. However, it is to beappreciated that footwear 10 need not be limited to such an orientation.Thus, in FIG. 1, rearwardly is toward heel portion 24 (to the right asseen in FIG. 1), forwardly is toward forefoot portion 20 (to the left asseen in FIG. 1), and downwardly is toward the bottom of the page as seenin FIG. 1. Top refers to elements toward the top of the view in FIG. 1,while bottom refers to elements toward the bottom of the view in FIG. 1.Inwardly is toward the center of footwear 10, and outwardly is towardthe outer peripheral edge of footwear 10.

The component can be a sole component, such as a sole component 14depicted in FIGS. 1-5, that includes a thermoplastic copolyester foamdescribed herein. The component can be an insert such as insert 36 orinsert 60 depicted in FIGS. 4-5 that includes a thermoplasticcopolyester foam described herein. The sole components and inserts forsole components can be made partially or entirely of a thermoplasticcopolyester foam described herein. Any portion of a sole component or aninsert for a sole component can be made of a thermoplastic copolyesterfoam described herein. For example, first portion 26 of the solecomponent (optionally including the ground engaging lower surface 44,such as the plurality of projections 46 and/or the groove 48 surroundingthe projections), the entire insert 36, portions 62 or 64 of insert 60,a separate outsole component, or any combination thereof, can include athermoplastic copolyester foam as described herein. The sole componentsand inserts can be made by foaming thermoplastic copolyestercompositions as described herein, for example by injection molding or byinjection molding followed by compression molding as described herein.In some aspects, the thermoplastic copolyester foams can be formed byphysical foaming of the compositions. The thermoplastic copolyesterfoams and components can demonstrate improved physical propertiesincluding one or more of an enhanced energy efficiency or energy return,and enhanced split tear, a decreased specific gravity, or a combinationthereof.

Sole component 14, which is generally disposed between the foot of thewearer and the ground, provides attenuation of ground reaction forces(i.e., imparting cushioning), traction, and may control foot motions,such as pronation. As with conventional articles of footwear, solecomponent 14 can include an insole (not shown) located within upper 12.In some aspects, the sole component is an insole or sockliner or is amulti-component assembly including an insole or sockliner, can furtherinclude an insole or sockliner located within the upper, where theinsole or sockliner is formed entirely or partially of a thermoplasticcopolyester foam described herein. Articles of footwear described hereincan include an insole or sockliner formed entirely or partially of athermoplastic copolyester foam described herein.

As can be seen in FIG. 2, sole component 14 consists of a first portion26 having an upper surface 27 with a recess 28 formed therein. Uppersurface 27 is secured to upper 12 with adhesive or other suitablefastening means. A plurality of substantially horizontal ribs 30 isformed on the exterior of first portion 26. In certain aspects, ribs 30extend from a central portion of forefoot portion 20 on medial side 16rearwardly along first portion 26, around heel portion 24 and forwardlyon lateral side 18 of first portion 26 to a central portion of forefootportion 20.

First portion 26 provides the external traction surface of solecomponent 14. In certain aspects it is to be appreciated that a separateoutsole component could be secured to the lower surface of first portion26. When a separate outsole component is secured to the lower surface offirst portion 26, the first portion 26 is a midsole component. In someaspects, the article is a midsole component for an article of footwear.In other aspects, the article is a combination midsole-outsole componentfor an article of footwear.

The article can be an insert. An insert 36 can be received in recess 28.As illustrated in FIG. 2, insert 36 can provide cushioning or resiliencyin the sole component. First portion 26 can provide structure andsupport for insert 36. In such aspects, first portion 26 can be formedof a material of higher specific gravity and/or hardness as compared toinsert 36 such as, for example, non-foam materials including rubber andthermoplastic polyurethane, as well as foam materials. In certainaspects, insert 36 can be formed of a thermoplastic copolyester foam asdisclosed herein.

Insert 36 has a curved rear surface 38 to mate with curved rear surface32 of recess 28 and a transverse front surface 40 to mate withtransverse front surface 34 of recess 28. An upper surface 42 of insert36 is in contact with and secured to upper 12 with adhesive or othersuitable fastening means. For example, when there is an insert 36, arecess 28 can extend from heel portion 24 to forefoot portion 20. Incertain aspects, the rear surface 32 of recess 28 is curved tosubstantially follow the contour of the rear of heel portion 24 and thefront surface 34 of recess 28 extends transversely across first portion26.

As seen best in FIG. 3, a ground engaging lower surface 44 of firstportion 26 includes a plurality of projections 46. Each projection 46 issurrounded by a groove 48. A plurality of transverse slots 50 are formedin lower surface 44, extending between adjacent projections 46. Alongitudinal slot 52 extends along lower surface 44 from heel portion 26to forefoot portion 20.

FIGS. 4 and 5 show bottom and top views of an insert 60 which can beused in a sole component as described herein. Insert 60 is similar toinsert 36, but as illustrated in FIGS. 4 and 5, insert 60 is formed oftwo types of materials 62 and 64, where at least one of the materials isa thermoplastic copolyester foam as disclosed herein. FIG. 4 shows abottom view of insert 60, while FIG. 5 shows a top view of insert 60formed of two types of materials 62 and 64, with the insert placedinside a first portion 66 to form a sole component 14. Inserts with morethan two types of materials, at least one of which is a thermoplasticcopolyester foam as disclosed herein, can also be used. In the exampleillustrated in FIGS. 4 and 5, a portion of a first material 62 can beused in the heel region of the insert, and a portion of a secondmaterial 64 can be used in the toe region of the insert. A higherspecific gravity material can be used to support the heel region, whilea lower specific gravity material can be used to support the toe region.For example, the specific gravity of the first material can be at least0.02 units greater than the specific gravity of the second material. Theshape of the portions of the two materials 62 and 64 of the insert canbe any suitable shape. For example, the heel region can be in the shapeof a wedge. Inserts formed of two types of materials can be useful inrunning shoes, as well as in basketball shoes.

In the articles comprising the foam articles or components including thethermoplastic copolyester microcellular open-cell or closed-cell foamand the layer of a second polymeric material disposed on at least aportion of an exterior surface of the foam as described herein.Referring to FIG. 7, in an aspect, a foam component 70 can have a foamportion 72, comprising a polymeric material that comprises athermoplastic copolyester microcellular open-cell or closed-cell foam.The foam portion 72 has one or more sides that, when the foam component70 is disposed in an article such as an article of footwear, areoriented toward an exterior facing side or surface of the article (e.g.an outer peripheral edge of article of footwear 10 of FIG. 1). Apolymeric layer 74 is disposed on at least a portion of an exteriorfacing side or surface of the foam portion 72. The polymeric layer 74comprises a second polymeric material that may be the same as ordifferent from the polymeric material of the foam portion 72. Accordingto aspects, the polymeric layer 74 is not a foamed material. Thepolymeric layer 74 can function as an outsole, for example, which canprovide improved abrasion resistance on one or more surfaces of the foamportion 72.

In some aspects, the article can be something other than a solecomponent. For example, the article can be an upper or an uppercomponent. An upper component refers to a piece that is stitched orotherwise joined with one or more other pieces to form an upper. Thematerials in the upper generally contribute to characteristics such asbreathability, conformability, weight, and suppleness or softness. Alower component refers to a piece that is joined with one or more otherpieces to form the lower portion of an article of footwear. The lowercan include, for example, the outsole and midsole. The choice of outsolematerials and design will contribute, for instance, to the durability,traction, as well as to the pressure distribution during use. Themidsole materials and design contribute to factors such as thecushioning and support. Grindery components include all of theadditional components that can be attached to the upper, lower, or both.Grindery components can include, for example, eyelets, toe puffs,shanks, nails, laces, velcro, catches, backers, linings, padding, heelbackings, heel foxings, toe caps, etc.

The upper can be a lasted upper. A “lasted upper,” as used herein,refers to an upper that is formed into the shoe shape prior toattachment to the sole by one or more mechanical means. The lasted uppercan include a heel counter formed to shape the heel of the upper. Thelasted upper can include a strobel or a strobel board attached to theupper, typically via a strobel stitch.

While the thermoplastic copolyester microcellular open-cell orclosed-cell foams described herein can be used for making any of avariety of components, including a variety of components for an articleof footwear, in particular aspects the components include a midsole, anoutsole, an insole, or an insert. Additional articles can include atongue padding, a collar padding, and a combination thereof. Asdescribed above and detailed more completely below, the articlescomprising the thermoplastic copolyester foams described herein canexhibit a unique balance of beneficial physical properties such as highenergy efficiency or energy return, high split tear, low specificgravity, and low compression. Furthermore, the thermoplastic copolyesterfoam can also be reprocessed with minimal loss in physical properties(e.g., for recycling), providing a solution for materialssustainability.

In some instances a disclosed article can comprise a first componentcomprising a foamed thermoplastic copolyester composition and a secondcomponent comprising a second polymeric material. An article comprisingthe first component with the second polymeric material can becharacterized by good bonding strength between the second polymericmaterial and the foam component. The ply adhesion strength between thesecond polymeric material and the foam component is greater than 2.5 kgforce/centimeter or greater than 3.0 kg force/centimeter, whendetermined using the Ply Adhesion Test method described herein.

First Components.

The first component is a foam component comprising a thermoplasticcopolyester composition. The first component can be a component such as,but not limited to, a component of a midsole or a midsole component. Itis understood that the first component comprises a foamed thermoplasticcopolyester composition. i.e. For example, a thermoplastic copolyestercomposition includes at least 90 weight percent, or at least 95 weightpercent, or at least 99 weight percent of the thermoplastic copolyesterdisclosed herein, based on the total weight of the thermoplasticcopolyester composition. In some instances, the polymeric component ofthe thermoplastic copolyester composition includes essentially only oneor more disclosed thermoplastic copolyester.

Second Components.

The second component comprising a second polymeric composition can be acomponent such as, but not limited to, a component of an outsole or anoutsole component. It is understood that the second component can befoamed, partially foamed, or essentially non-foamed. In some instancesthe second component is foamed component, i.e., a second foam component.In other instances, the second component is an unfoamed component, i.e.,a solid component. The second polymeric composition comprises adisclosed second polymeric material. In some instances, the secondpolymeric material is a disclosed thermoplastic copolyester composition.For example, a second polymeric material can include at least 90 weightpercent, or at least 95 weight percent, or at least 99 weight percent ofthermoplastic copolyesters disclosed herein, based on the total weightof the second polymeric material. In some instances, the secondpolymeric material includes essentially only one or more disclosedthermoplastic copolyesters. In other instances, the second polymericmaterial can include a polymeric material essentially free of adisclosed thermoplastic copolyester, e.g., a thermoplastic elastomer orthermoplastic vulcanizate material as disclosed herein. In still otherinstances, a second polymeric material can include a mixture of adisclosed thermoplastic copolyester and a polymeric material that is nota disclosed thermoplastic copolyester, e.g., a thermoplastic elastomeror thermoplastic vulcanizate material.

Characteristics of Thermoplastic Copolyester Foam Components.

As discussed herein above, a first component can be foam component,i.e., a first foam component, comprising a disclosed thermoplasticcopolyester. In some instances, a second component can be foamcomponent, i.e., a second foam component, comprising a disclosedthermoplastic copolyester. That is, each of the first or second foamcomponents can independently comprise a disclosed thermoplasticcopolyester foam component. It is understood herein throughout thatreference to a “thermoplastic copolyester foam” is inclusive of a firstfoam component, a second component, or both a first and a second foamcomponents, and that each of the first and second foam components canindependently comprise one or more disclosed thermoplastic copolyesterpolymeric materials as disclosed herein below. A disclosed thermoplasticcopolyester foam can exhibit various beneficial properties.

For example, the thermoplastic copolyester foam can exhibit a beneficialsplit tear, for example a high split tear for a sole component in anarticle of footwear. In some aspects, the thermoplastic copolyester foamcan have a split tear value of greater than about 1.5kilogram/centimeter (kg/cm), or greater than about 2.0 kg/cm, or greaterthan about 25 kg/cm, when determined using the Split Tear Test Methoddescribed herein. In some aspects, the thermoplastic copolyester foamcan have about 1.0 kg/cm to 4.5 kg/cm, about 1.5 kg/cm to 4.0 kg/cm,about 2.0 kg/cm to 4.0 kg/cm, about 2.0 kg/cm to 3.5 kg/cm, or about 2.5kg/cm to 3.5 kg/cm, when determined using the Split Tear Test methoddescribed herein. In some aspects, the thermoplastic copolyester foam isinjection molded (i.e., is not exposed to a separate compression moldingstep after being formed by injection molding and removed from theinjection mold), or is injection molded and subsequently compressionmolded in a separate compression mold having different dimensions thanthe mold used in the injection molding step. The thermoplasticcopolyester foam can have a split tear of about 0.08 kg/cm to 4.0 kg/cm,about 0.9 kg/cm to 3.0 kg/cm, about 1.0 to 2.0 kg/cm, about 1.0 kg/cm to1.5 kg/cm, or about 2 kg/cm. In some aspects, the thermoplasticcopolyester foam the thermoplastic copolyester foam is injection molded,and has have a split tear of about 0.07 kg/cm to 2.0 kg/cm, or about 0.8kg/cm to 1.5 kg/cm, or about 0.9 to 1.2 kg/cm, about 1.5 kg/cm to 2.2kg/cm.

The specific gravity of a disclosed thermoplastic copolyester foam isalso an important physical property to consider when using a foam for inan article of footwear or athletic equipment. As discussed above, thethermoplastic copolyester foam of the present disclosure exhibits a lowspecific gravity, which beneficially reduces the weight of midsoles orother components containing the thermoplastic copolyester foam. Thethermoplastic copolyester foams of the present disclosure can have aspecific gravity of from 0.02 to 0.22, or of from 0.03 to 0.12, or offrom 0.04 to 0.10, or from 0.11 to 0.12, or from 0.10 to 0.12, from 0.15to 0.2; 0.15 to 0.30, when determined using the Specific Gravity TestMethod described herein. Alternatively or in addition, the thermoplasticcopolyester foam can have a specific gravity of from 0.01 to 0.10, or offrom 0.02 to 0.08, or of from 0.03 to 0.06; 0.08 to 0.15; or from 0.10to 0.12, when determined using the Specific Gravity Test Methoddescribed herein. For example, the specific gravity of the thermoplasticcopolyester foam can be from or from 0.15 to 0.2, or can be from 0.10 to0.12. The thermoplastic copolyester foam can be injection molded, or canbe injection molded and subsequently compression molded. In someaspects, the thermoplastic copolyester foam has a specific gravity ofabout 0.7 or less, or 0.5 or less, or 0.4 or less, or 0.3 or less, whendetermined using the Specific Gravity Test Method described herein. Insome aspects, the thermoplastic copolyester foam, includingthermoplastic copolyester foam present in midsoles and midsolecomponents, can have a specific gravity of about 0.05 to 0.25, about0.05 to 0.2, about 0.05 to 0.15, about 0.08 to 0.15, about 0.08 to 0.20,about 0.08 to 0.25, or about 0.1 to 0.15, when determined using theSpecific Gravity Test Method described herein. In some aspects thethermoplastic copolyester foam has a specific gravity of about 0.15 to0.3, about 0.2 to 0.35, or about 0.15 to 0.25, when determined using theSpecific Gravity Test Method described herein.

The thermoplastic copolyester foam portion of the article or componentof an article can have a stiffness of about 200 kPa to about 1000 kPa,or about 300 to about 900 kPa or about 400 to about 800 kPa or about 500to about 700 kPa, when determined using the Cyclic Compression Test withthe 45-millimeter diameter cylindrical sample. The thermoplasticcopolyester foam portion of the article or component of an article canhave a stiffness of about 200 kPa to about 1000 kPa, or about 300 toabout 900 kPa or about 400 to about 800 kPa or about 500 to about 700kPa, when determined using the Cyclic Compression Test with the footformsample. The thermoplastic copolyester foam article or article componentcan be formed by injection molding, or by injection molding andsubsequently compression molding.

The thermoplastic copolyester foam portion of the article or componentof an article can have an Asker C durometer hardness of from about 30 toabout 50, or from about 35 to about 45, or from about 30 to about 45, orfrom about 30 to about 40, when determined using the Durometer HardnessTest described herein

The energy input of a foam is the integral of the force displacementcurve during loading of the foam during the Cyclic Compression test. Theenergy return of a foam is the integral of the force displacement curveduring unloading of the foam during the Cyclic Compression test. Thethermoplastic copolyester foam portion of the article or component of anarticle can have an energy return of about 200 millijoules (mJ) to about1200 mJ, or from about 400 mJ to about 1000 mJ, or from about 600 mJ toabout 800 mJ, when determined using the Cyclic Compression Test with a45-millimeter diameter cylindrical sample.

The energy efficiency, a measure of the percentage of energy thethermoplastic copolyester foam portion of the article or componentreturns when it is released after being compressed under load, canprovide improved performance for athletic shoes, e.g. for reducingenergy loss or dissipation when running. This is especially true forrunning and other athletic shoes. In some aspects, the thermoplasticcopolyester foam portion of the articles and components provided hereinhave an energy efficiency of about 50 percent to 97 percent, about 60percent to 95 percent, about 60 percent to 90 percent, about 60 percentto 85 percent, about 65 percent to 85 percent, or about 70 percent to 85percent, when determined using the Cyclic Compression Test with a45-millimeter diameter cylindrical sample.

In particular examples, the energy efficiency of the subsequentlycompression molded thermoplastic copolyester foam can be at least atleast 6 percentage points, or at least 7 percentage points, or at least8 percentage points, or at least 9 percentage points, or at least 10percentage points, or at least 12 percentage points greater than theenergy efficiency of the injection molded thermoplastic copolyester foamwhich has not subsequently been compression molded, when the compressionmolded thermoplastic copolyester foam has an energy efficiency greaterthan 45 percent, or greater than 50 percent, or greater than 55 percent,or greater than 60 percent, or greater than 65 percent, and thecompression molded thermoplastic copolyester foam can have a specificgravity of from 0.02 to 0.15, or of from 0.03 to 0.12, or of from 0.04to 0.10 or from 0.11 to 0.12, from 0.15 to 0.2; or 0.15 to 0.30.

The resulting foams can have a microcellular closed-cell or open-cellfoam structure. Cells are the hollow structures formed during thefoaming process, in which bubbles are formed in the polymeric materialby the blowing agents. The cell walls are generally defined by thepolymeric material. The cells can be entirely enclosed by the polymericmaterial, or they can be at least partially open, e.g., interconnectedwith one or more adjacent cells. “Closed-cell” structures refer tostructures in which at least 60 percent or more of the cells are closedcells, or at least 80 percent of the cells are closed cells, or at least90 percent of the cells are closed cells, or at least 95 percent of thecells are closed cells. As described herein “open-cell” structuresrefers to foam structures in which less than about 5 percent or lessthan 4 percent, or less than 3 percent or less than 1 percent of thecells are closed cells.

The disclosed foams may have a cell diameter of from about 50 micrometerto about 1000 micrometer, or from about 80 micrometer to about 800micrometer, or from about 100 micrometer to about 500 micrometer.

The proportion of cells in the foam having a cell diameter of about 50micrometer to about 1000 micrometer is preferably not less than 40percent relative to all the cells, or not less than 50 percent or notless than 60 percent relative to all the cells. If the proportion ofcells is less than 40 percent, the cell structure will tend to benonuniform and/or have a coarse cell structure. As used herein, a“coarse cell structure” refers to a foam structure in which the averagecell diameter is greater than 1 millimeter, and/or for greater than 20percent of the cells, a 1 millimeter line drawn across the largestdimension of the cell, will not cross a cell wall or a strut (i.e., anopen cell wall or portion thereof).

The number of open cells and/or closed cells and cell diameter of thecells of the foam can be determined visually, for example by capturingan image of a cut surface with a camera or digital microscope,determining the number of cells, number of open cells and/or number ofclosed cells, and determining an area of a cell, and converting it tothe equivalent circle diameter.

Methods of Manufacturing Disclosed Foams.

In some examples, the disclosed foamed polymeric materials can beprepared by various methods as disclosed herein and as known in the art.That is, disclosed articles or components of articles such as midsoles,midsole components, inserts and insert components can be prepared byinjection molding a melt composition comprising a polymeric material asdescribed herein using a physical blowing agent and/or chemical blowingagent. A disclosed foam component, e.g., a disclosed first foamcomponent or a disclosed foam second foam component, can be prepared bythe methods disclosed herein below.

Disclosed herein are methods for making a foam article or component, themethod comprising: forming a mixture of molten polymeric material and ablowing agent, wherein the polymeric material comprises a disclosedthermoplastic copolyester; injecting the mixture into a mold cavity;foaming the molten polymeric material, thereby forming a foamed moltenpolymeric material; solidifying the foamed molten polymeric material,thereby forming a foam article having a microcellular foam structure;and removing the foam article from the mold cavity.

Also disclosed are methods for making a foam article or component, themethod comprising: forming a mixture of molten polymeric material and ablowing agent, wherein the polymeric material comprises a disclosedthermoplastic copolyester; injecting the mixture into a mold cavity;foaming the molten polymeric material, thereby forming a foamed moltenpolymeric material; solidifying the foamed molten polymeric material,thereby forming a foam article having a microcellular foam structure;and removing the foam article from the mold cavity; wherein the mixturehas an injection temperature; and wherein the injection temperature isfrom about the melting temperature of the thermoplastic copolyester toabout 50 degrees C. above the tail temperature of the thermoplasticcopolyester.

Also disclosed are methods for making a foam article or component, themethod comprising: forming a mixture of molten polymeric material and ablowing agent, wherein the polymeric material comprises a disclosedthermoplastic copolyester; injecting the mixture into a mold cavity;foaming the molten polymeric material, thereby forming a foamed moltenpolymeric material; solidifying the foamed molten polymeric material,thereby forming a foam article having a microcellular foam structure;and removing the foam article from the mold cavity; wherein the foamingoccurs at a foaming temperature; and wherein the foaming temperature isfrom about the melting temperature of the thermoplastic copolyester toabout 50 degrees C. above the tail temperature of the thermoplasticcopolyester.

Dynamic scanning calorimetry (DSC) is used to determine the meltingtemperature and the tail temperature of a thermoplastic copolyester, andan exemplary method is described herein below. Briefly, 10-30 mg piecesof undried resin pellets are cycled from −90 degrees C. to 225 degreesC. at 20 degrees C./min and cooled to −90° C. at 10° C./min. In someinstances, experiments are run using a heat-cool-heat profile with aramp rate of 10 degrees C. per min, minimum temperature of 0 degrees C.and maximum temperature of 250 degrees C. Analyses should be determinedin duplicate. The T_(m) and T_(g) values are recorded from the secondcycle. The melt “peak” is identified as the local maximum of the secondheating cycle. If there is more than one peak in the DSC curve, the peakoccurring at hotter temperatures is chosen as the temperature reference.The tail is identified as the intersection of the tangent of the line ofthe higher temperature side of the melt peak with the extrapolatedbaseline. A schematic illustrating the method for determining peak andtail temperatures is shown in FIG. 8.

For example, the disclosed foamed polymeric materials can be preparedusing a suitable extruder. An extruder (e.g., single or twin screw) canbe used to provide a composition. The extruder can have a motor to turna screw inside the extruder. Extruder may be a single screw or twinscrews made of individual elements of various sizes and pitchesappropriate for mixing or kneading the specific materials used. In someexamples, the extruder has a twin screw.

The various components that make up the compositions used to form thethermoplastic copolyester foam of the various examples described hereinare added into the extruder through one or more port. The variouscomponents can be added as a melt or as appropriately-sized solidparticles, for example chips or pellets, that are melted in section asthey are mixed in the barrel of the extruder. The contents of theextruder can be heated to melt the composition. A supercritical fluidcan be added into the melt as a physical blowing agent. In particularexamples, the thermoplastic copolyester foam is prepared by using aphysical blowing agent which foams the composition after it exits theextruder, and the thermoplastic copolyester foam is thus substantiallyfree of a chemical blowing agent or decomposition product thereof.

The compositions can be added as a melt at a temperature close to themelting temperature of the polymeric component of the composition.

If a chemical blowing agent is used, the processing (melting)temperature used can be sufficiently below the temperature that wouldtrigger the blowing agent. In order to foam the composition, thetemperature near the exit of the extruder can be increased to atemperature close to or at the triggering temperature of a chemicalblowing agent, thereby producing a chemically foamed thermoplasticcopolyester foam as the composition exits the extruder (e.g., as thecomposition is injected into an injection mold).

Alternatively or in addition, a physical blowing agent can be used forfoam the composition to form a physically foamed thermoplasticcopolyester foam, or a physically and chemically foamed thermoplasticcopolyester foam. For example, a supercritical fluid such assupercritical carbon dioxide or supercritical nitrogen can be mixed withthe molten polymeric composition in the barrel of the extruder to form asingle-phase solution. As the single-phase solution exits the extruder,the pressure drop between the higher pressure in the extruder and thelower pressure outside the extruder causes the supercritical fluid totransition to the gas phase and foam the molten polymeric composition.

Various examples include methods of manufacturing an article of footwearor components for an article of footwear. In some examples, the methodsof manufacturing an article of footwear include injection molding acomposition to form a thermoplastic copolyester foam described herein toproduce a foam article or component of an article, such as an article offootwear. The article or component of an article can be a midsole or acomponent of a midsole, and the method can include providing an upperand an outsole for an article of footwear; and combining the midsole ormidsole component, the upper, and the outsole to make an article offootwear. In some examples, the method of manufacturing the article offootwear includes combining an article comprising a thermoplasticcopolyester foam, an upper, and an outsole to make an article offootwear.

The articles or components of articles such as midsoles, midsolecomponents, inserts and insert components can be prepared by injectionmolding a melt composition described herein using a physical blowingagent. The injection molding can use a screw-type injector that allowsfor maintaining and controlling the pressure in the injector barrel. Theinjection molding machine can allow metering and delivering asupercritical fluid such as carbon dioxide or nitrogen into thecomposition prior to injection. The supercritical fluid can be mixedinto the composition within the injection barrel and then injected intothe mold. The supercritical fluid can then expand to create cell nucleito form the physical foam within the mold. The injection molding caninclude physical foaming of the compositions described herein using amicrocellular foam injection molding process, such as, for example the“MUCELL” process (Trexcel Inc., Royal Oak. Mich., USA).

The thermoplastic copolyester foams described herein can be made using aprocess that involves impregnating a polymeric composition (e.g., at orabove a softening temperature of the composition) with a physicalblowing agent at a first concentration or first pressure. As usedherein, the term “impregnating” generally means dissolving or suspendinga physical blowing agent in a composition. The impregnated compositioncan then be foamed, or can be cooled (when applicable) and re-softened(when applicable) for blowing at a later time. In particular examples,the impregnated composition is a single-phase solution comprising carbondioxide or nitrogen and the molten thermoplastic copolymer composition.

The impregnated composition is foamed by reducing the solubility of thephysical blowing agent in the polymer matrix through pressure ortemperature changes. The reduction in solubility of the physical blowingagent can release additional amounts (e.g., to create a secondaryexpansion of an originally-formed microcell in the composition) of theimpregnated physical blowing agent from the composition, to further blowthe composition, forming a foam composition (e.g., a foam compositionhaving a microcellular structure).

In addition to injection molding, the thermoplastic copolyester foam ofthe present disclosure can be foamed and molded using various processesknown in the art. For example, the thermoplastic copolyester foam can beformed into slab foam, filament or strand foams, particulate (e.g.,bead) foams of various shapes and sizes, etc. These various forms offoam can then be used in different ways. For example, like injectionmolded foam, slab foam and filament or strand foam can be used directlyas a finished foam article, or can be shaped (e.g., cut, buffed, ortrimmed) to form a finished foam article, or can be compression moldedto form a finished foam article. Optionally, the thermoplasticcopolyester foam can be subjected to annealing processes as part offorming the finished foam article. Pellets of the compositions can beused to form individual particulate thermoplastic copolyester foams, orcan be foamed and molded to form unitary molded foam articles composedof individual portions of foam affixed to each other.

The thermoplastic copolyester foams of the various examples describedherein may be further shaped or molded by any of the methods known forforming articles from thermoplastic materials. Optionally, thethermoplastic copolyester foams of the present disclosure which havebeen foamed using any suitable blowing process (e.g., blowing using aphysical and/or chemical blowing agent), including by injection moldingusing only a physical blowing agent, can then be compression molded toform a compression molded foam.

The thermoplastic copolyester foam of the present disclosure can beprepared by a process comprising (i) softening a composition (e.g., byheating at a first temperature at or above a softening temperature ofthe composition); (ii) simultaneously or sequentially with the softening(when applicable), contacting the composition with a first concentrationor first pressure of a physical blowing agent sufficient to drive anamount of the physical blowing agent into the composition or combine thephysical blowing agent with the composition; (iii) changing theconcentration or pressure (e.g., decreasing the pressure orconcentration) of the physical blowing agent to a second concentrationor second pressure that is effective to foam the composition, therebyforming a thermoplastic copolyester foam (e.g., a thermoplasticcopolyester foam having a microcellular structure); and, (iv) followingthe changing, cooling (when applicable) the thermoplastic copolyesterfoam to (e.g., cooling to a temperature below the softening temperatureof the composition), to form a solidified thermoplastic copolyesterfoam.

The thermoplastic copolyester foam of the present disclosure can beprepared by (i) contacting (e.g., dissolving or suspending) thecomposition with a first concentration of a chemical blowing agent, insome examples, at or above a softening temperature of the composition(ii) triggering the chemical blowing agent to foam the composition,thereby forming a thermoplastic copolyester foam (e.g., a thermoplasticcopolyester foam having a microcellular structure); and, (iii) followingthe triggering, in some examples, cooling the thermoplastic copolyesterfoam to, e.g., a temperature below its softening temperature, to form asolidified thermoplastic copolyester foam. In some examples, the“triggering” of the chemical blowing agent is performed by any suitablemethod, including heating the composition comprising a concentration ofthe chemical blowing agent to a temperature sufficient to “trigger” thechemical blowing agent, wherein the concentration of the chemicalblowing agent is effective to foam the composition, thereby forming athermoplastic copolyester foam (e.g., a thermoplastic copolyester foamhaving a microcellular structure). In some examples, the contactingcomprises contacting at a pressure of from about 10 MPa to about 100 MPa(e.g., from about 30 MPa to about 100 MPa, about 20 MPa to about 80 MPa,about 30 MPa to about 60 MPa or about 40 MPa to about 70 MPa).

Chemical foaming agents may be endothermic or exothermic, which refersto a type of decomposition they undergo to produce the gas for foaming.The decomposition may be a result of thermal energy in the system.Endothermic foaming agents absorb energy and typically release a gas,such as carbon dioxide, upon decomposition. Exothermic foaming agentsrelease energy and generate a gas, such as nitrogen, when decomposed.Regardless of the chemical foaming agent used, thermal variables of thepolymer composition being molded and thermal variables of the foamingagent to be decomposed are coupled together such that process parametersare selected so that the polymer can be molded and the foaming agent candecompose at an appropriate phase of the molding operation.

The disclosed foamed polymeric materials and articles can be prepared byusing systems such as those disclosed in U.S. Patent Appl. No.62/734,912, which is incorporated herein by reference. Briefly, thesystem provides for decreased pressure losses across the system as wellas to control (e.g., deliberately increase or decrease) the elongation,apparent shear, and/or zero shear viscosities of the molten polymericmaterial that is flowed into the mold. The method includes flowing amolten polymeric material into a shot tuning chamber from an upstreamdevice and adjusting a temperature, a pressure, or both, within the shottuning chamber to create a tuned molten polymeric material. The methodadditionally includes flowing the tuned molten polymeric material into amold cavity from the shot tuning chamber. It will be appreciated thatfine-tuning the temperature of and/or pressure applied to the moltenpolymeric material enables the system to have a desired impact on thephysical and mechanical properties of the molded article. In particular,the temperature of the molten polymeric material may be controlled toachieve a desired range of shear/extensional viscosities, which reduces(e.g., substantially eliminates) uncontrolled bubble growth and/ornucleation. In one example, the method may also include adjusting (e.g.,increasing and/or decreasing) a pressure in the mold cavity via a gascounter pressure (GCP) assembly prior to or while the molten polymericmaterial is flowed from the shot tuning chamber into the mold cavity. Insuch an example, the molten polymeric material may be flowed into themold cavity at pressures well above ambient pressure. Furthermore, GCPmay be introduced into the mold cavity to control nucleation and bubblegrowth during polymer foaming as well as increase surface quality of themolded article. Nucleation and bubble growth control enhances celldensity uniformity and mechanical properties of the molded polymericmaterial. In some examples, the improvement in cell density homogeneitymay be particularly beneficial in articles having low densities such asarticles that have a density less than or equal to 0.3 grams per cubiccentimeter and/or in articles having large dimensions such as articleshaving a thickness that is 1.0 cm, for instance.

The system can include a shot tuning chamber configured to receive amolten polymeric material from an upstream device. The shot tuningchamber is also configured to adjust one or more of a temperature of anda pressure applied to the molten polymeric material to create anadjusted molten polymeric material and to dispense the adjusted moltenpolymeric material. In this way, the system can selectively adjusttuning chamber temperature and/or pressure to achieve desiredproperties, as previously mentioned. In one example, the system mayfurther include an adjustable mold runner configured to regulate fluidiccommunication between the shot tuning chamber and a mold cavity in amold. In another example, the system can further include a GCP assemblycoupled to the mold cavity and configured to regulate an amount ofcounter pressure gas flow into and out of the mold cavity. Providing GCPadjustment allows for additional tuning of the polymeric material as itenters and cools in the mold.

Alternatively, the disclosed foamed polymeric materials and articles canbe prepared using methods and systems as described in InternationalPatent Appl. No. PCT/US2018/035128. Briefly, the method can comprise amethod for molding a single-phase solution comprised of a polymercomposition and a gas. The polymer composition and the gas aremaintained under pressure during the molding operation to prevent acellular structure from being formed by the dissolved gas in the polymercomposition coming out of solution. The mold cavity in which thesingle-phase solution is introduced for molding purposes is pressurizedto a mold pressure that is sufficient to maintain the single-phasesolution as a single-phase solution as the mold cavity is filled.Subsequent to filling the mold cavity with the single-phase solutionunder pressure, the resulting article may solidify entrapping thecompressed gas, or the article may be exposed to a reduction in pressurecausing the entrapped gas to form a microcellular structure.

The method can include forming the single-phase solution, such asthrough introduction of pressurized gas with a polymer composition thatis melted, e.g., from about the T_(m) up to about 50 degrees C. abovethe T_(tail) of the thermoplastic copolyester as described elsewhere, inan injection molding apparatus's barrel (e.g., screw) that is effectiveto mix and dissolve the gas with the polymer composition while underpressure. The method continues with pressurizing a mold cavity of a moldabove atmospheric pressure to a mold pressure. Atmospheric pressure is apressure of the environment in which the mold cavity is exposed (e.g.,general environment pressure). The mold pressure is at least a pressureto maintain the single-phase solution as a single single-phase. Themethod further includes injecting the single-phase solution into thepressurized mold cavity. The method also includes maintaining at leastthe mold pressure in the mold cavity during the injecting of thesingle-phase solution. As a result, the pressure in the mold cavityprevents the gas from coming out of solution to form a two-phase mixture(e.g., foaming) upon exit from the injection molding apparatus. As thepressure is maintained, premature foaming as the polymer composition isinjected from the injection molding apparatus is avoided to allow adecoupling of process parameters associated with the foaming agent andthe polymer composition.

A molding system can be utilized to prepare the disclosed foamedpolymeric materials that includes a device configured to receive apolymeric material and heat the polymeric material to form a moltenpolymeric material. The molding system additionally includes a shottuning chamber configured to receive the molten polymeric material fromthe device and adjust a temperature of or a pressure applied to themolten polymeric material. The molding system also includes anadjustable mold runner configured to regulate the flow of the moltenpolymeric material between the shot tuning chamber and a mold cavity. Inone example, the device may be an injection device or an extrusiondevice. The molding system allows the characteristics of the polymericmaterial to be adapted to achieve desired end-use goals.

In some aspects, the present disclosure is directed to a compressionmolded thermoplastic copolyester foam, and to a method of formingcompression molded thermoplastic copolyester foam for, among otherapplications, articles of footwear or athletic equipment. In someexamples, the method can be a process comprising providing (e.g.,preparing) a thermoplastic copolyester foam preform and then compressionmolding the thermoplastic copolyester foam preform to form a compressionmolded thermoplastic copolyester foam. For example, the thermoplasticcopolyester foam can be compression molded by placing the thermoplasticcopolyester foam preform in a compression mold having a height less thanthe initial height of the thermoplastic copolyester foam preform andclosing the mold, thereby compressing the thermoplastic copolyester foampreform to the height of the mold. Simultaneously or sequentially withthe compressing, the thermoplastic copolyester foam preform can beheated in the closed compression mold. During the compression molding,the temperature of at least a portion of the thermoplastic copolyesterfoam preform in the closed mold can be raised to a temperature within±30 degrees C. of the softening temperature of the composition. Thetemperature can be raised by heating the closed mold. Following theraising of the temperature, while the thermoplastic copolyester foampreform remains closed in the compression mold, the temperature of atleast a portion of the thermoplastic copolyester foam preform can belowered. The temperature can be lowered by cooling the closed mold. Thelowering can lower the temperature of at least a portion of thethermoplastic copolyester foam preform to a temperature at least 35degrees C. below the softening temperature of the composition, therebyforming the compression molded thermoplastic copolyester foam. Followingthe cooling, the compression mold can be opened, and the compressionmolded thermoplastic copolyester foam can be removed from thecompression mold.

Examples contemplated herein are directed to methods of manufacturingarticles of footwear or athletic equipment. For example, the method cancomprise providing components such as midsoles and inserts of an articleof footwear in accordance with the present disclosure, and combining thecomponent with a footwear upper and an outsole to form the article offootwear.

One method of making compression molded thermoplastic copolyester foamarticles such as midsoles and inserts or components of articles such ascomponents of midsoles or components of inserts described hereincomprises forming a thermoplastic copolyester foam preform andcompression molding the thermoplastic copolyester foam preform to make acompression molded thermoplastic copolyester foam. In some examples, thefoam preforms of the various examples described herein are obtained byblowing the composition by about 150 percent to about 240 percent (e.g.,from about 150 percent to about 220 percent; about 150 percent to about200 percent, about 175 percent to about 225 percent, about 180 percentto about 230 percent or about 160 percent to about 240 percent) in atleast one dimension (e.g., the vertical dimension) using a blowingagent. In some examples, the blown composition can be compression moldedto about 120 percent to about 200 percent (e.g., from about 120 percentto about 180 percent; about 130 percent to about 190 percent; about 150percent to about 200 percent; or about 160 percent to about 190 percent)in at least one dimension.

Thus for example, if the foaming of the composition is about 200percent, the blown composition can be compression molded by a net 20percent by compression molding to about 180 percent. In another example,if the composition is blown into a 20 millimeter (height)×10 centimeter(width)×5 centimeter (depth) slab (wherein hereinafter, “mm” will beused to indicate millimeter and “cm” will be used to indicatecentimeter), and the slab is compression molded in the height directionby 20 percent, the compression molded slab would have the dimensions 18mm (height)×10 cm (width)×5 cm (depth). In some examples, thecompression molding is substantially maintained.

The thermoplastic copolyester foam can be made using a process thatinvolves impregnating a composition (e.g., at or above a softeningtemperature of the composition) with a physical blowing agent at a firstconcentration or first pressure. The impregnated composition can then befoamed, or can be cooled (when applicable) and re-softened (whenapplicable) for blowing at a later time. In some instances, theimpregnated composition is foamed by reducing the temperature orpressure, impacting the solubility of the physical blowing agent. Thereduction in solubility of the physical blowing agent can releaseadditional amounts of the impregnated physical blowing agent from thecomposition to further blow the composition forming a thermoplasticcopolyester foam (e.g., a thermoplastic copolyester foam having amicrocellular structure).

The compression molding process can be conducted by heating thethermoplastic copolyester foam preform in a closed compression mold. Thethermoplastic copolyester foam preform is heated to a temperature closeto its softening temperature, to allow the foam to retain the shape ofthe compression mold. For example, the foam preform can be heated to atemperature within plus or minus 30 degrees C. of its softeningtemperature, or within plus or minus 20 degrees C. of its softeningtemperature, or within plus or minus 10 degrees C. of its softeningtemperature, or within plus or minus 5 degrees C. of its softeningtemperature. For example, the thermoplastic copolyester foam preform canbe heated to a temperature of from about 100 degrees C. to about 250degrees C., or of from about 140 degrees C. to about 220 degrees C., orof from about 100 degrees C. to about 150 degrees C., or of from about130 degrees C. to about 150 degrees C.

The material used to form the compression mold can be any material whichcan withstand the temperatures used during the process, such as machinedmetals, including aluminum. The compression mold can be made using twopieces, such as a top and a bottom mold. Depending on the shape of thefoam component to be molded, a multiple-piece mold may be used in orderto more easily release the compression molded foam from the mold.

The injection molded thermoplastic copolyester foam can have a closedskin. A closed skin can be formed by foaming and molding a thermoplasticcopolyester foam in a closed mold. A closed skin can also be formed bycompression molding a thermoplastic copolyester foam preform in acompression mold. However, care should be taken during the compressionmolding not to subject the thermoplastic copolyester foam preform toconditions such that more than a desired amount of the closed cellstructures of the foam collapse. One way to avoid collapsing more than adesired amount of the closed cell structures is to control thetemperature of the thermoplastic copolyester foam during the compressionmolding process, for example, by controlling the temperature of themold. For example, during the compression molding step, the heating ofthe thermoplastic copolyester foam preform in the compression mold canbe conducted for time of from 100 seconds to 1,000 seconds, or of from150 seconds to 700 seconds.

Once the thermoplastic copolyester foam has been heated in thecompression mold at the appropriate temperature for the desired lengthof time to soften the thermoplastic copolyester foam to the desiredlevel, the softened preform is cooled, for example, to a temperature atleast 35 degrees C. below its softening temperature, or at least 50degrees C. below its softening temperature, or at least 80 degrees C.below its softening temperature, to re-solidify the softened foam,thereby forming the compression molded foam. Once cooled, thecompression molded thermoplastic copolyester foam is removed from thecompression mold. Following the heating, the cooling of the foam preformin the compression mold can be conducted for a time of from 50 to 1,000seconds, or for a time of from 100 to 400 seconds.

The thermoplastic copolyester foam can be foamed using any one of themethods described above. The thermoplastic copolyester foam can beincluded in components of articles of footwear as described above, forexample a midsole 146 as depicted in FIGS. 1A-1B.

Also disclosed herein are methods for preparation of foamed articles orcomponents having improved foam quality. In particular, disclosed hereinare methods for preparation of foamed articles or components comprisinginjection using high aspect ratio injection cavity molds. As understoodherein, the improved foam quality achieved using the high aspect ratioinjection cavity molds refers decreased voids, improved homogeneity offoam cell size distribution (i.e., more consistent foam structures), anda decrease in average foam cell size.

It has been found that the disclosed methods using higher aspect ratioinjection cavity molds provide more consistent foam structures comparedto low aspect ratio cavities. For 3D shapes, aspect ratio is definedherein as the ratio of the shape's maximum dimension to its minimumdimension. Thus, for regular shapes, (e.g., spheres, cubes, rectangles,cylinders, and the like), aspect ratio is defined herein aslength/width. However, for irregular shapes, such as those frequentlyencountered in injection molding of commercially useful articles orcomponents, such as, but not limited to, a midsole or a midsolecomponent, no single dimension accurately represents the shape in amanner similar to a regular shape. Accordingly, for irregular shapes,aspect ratio is defined herein as the ratio of the maximum distance fromthe center of mass of the equivalent solid of the shape to the surfaceof the shape (L_(max)) relative to the minimum distance from the samepoint to the surface (L_(min)). It is understood that injection cavitieswith multiple gates, the volume allocated to each gate can be consideredas having its own characteristic aspect ratio based on the fractionalvolume of the cavity it fills. Thus, the volume associated with eachgate can be calculated using appropriate software and based on thecalculated filled volume, an aspect ratio is readily calculated for eachgate.

Referring now to FIGS. 15A and 15B, which show cross-sectional top planviews for two different schematic representations of injection molds, 10and 11, respectively, showing a given cross-section through a mold andmold cavity therein. FIG. 15A shows a cross-sectional top plan view foran injection mold 10 having an injection cavity therein having aplurality of regions, i.e., a first region 20, a second region 21, athird region 22, and a fourth region 23, each of which is associatedwith one of a plurality of gates, i.e., a first gate 30, a second gate31, a third gate 32, and a fourth region 33. FIG. 15B shows across-sectional top plan view for an injection mold 11 having aninjection cavity therein having a plurality of regions, i.e., a firstregion 20, a second region 21, a third region 22, a fourth region 23, afifth region 24, and a sixth region 25, each of which is associated withone of a plurality of gates, i.e., a first gate 30, a second gate 31, athird gate 32, a fourth gate 33, a fifth gate 34, and a sixth region 35.That said, each region is associated with a volume that extends in thethird dimension above and below the cross-sectional plan view shown. Incomparing the injection cavity shown in each of FIGS. 15A and 15B, themold cavity shown in FIG. 15B has a higher aspect ratio one or more ofthe regions compared to the regions given for the mold cavity shown inFIG. 15A. In particular, the aspect ratio is higher in a first region20, a second region 21, a third region 22 of the mold cavity shown inFIG. 15B compared to an area roughly the same in size in FIG. 15A, i.e.,the first region 20 and a portion of the second region 21.

In various aspects, the aspect ratio for a higher aspect ratio injectioncavity mold is increased in at least one region by a factor of about1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7,about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9, about 3.0,about 3.1, about 3.2, about 3.3, about 3.4, about 3.5, about 3.6, about3.7, about 3.8, about 3.9, about 4.0, about 4.1, about 4.2, about 4.3,about 4.4, about 4.5, about 4.6, about 4.7, about 4.8, about 4.9, about5.0, about 5.1, about 5.2, about 5.3, about 5.4, about 5.5, about 5.6,about 5.7, about 5.8, about 5.9, about 6.0, about 6.5, about 7.0, about7.5, about 8.0, about 8.5, about 9.0, about 9.5, about 10; a rangeencompassed by any of the foregoing values; or any combination of theforegoing values.

Methods of Manufacturing Disclosed Articles.

Various examples include methods of manufacturing an article comprisinga first component and a second component. As discussed herein above, thefirst component can be a foam component, e.g., a first foam component,and the second component can be a foam component, e.g., a second foamcomponent. The first component can be, but is not limited to, a midsoleor component of a midsole. The second component can be, but is notlimited to, an outsole or an upper. It is understood that the secondcomponent can be foamed, partially foamed, or essentially non-foamed. Insome instances, the second polymeric material comprises one or moredisclosed thermoplastic copolyester compositions. For example, a secondpolymeric material includes at least 90 weight percent, or at least 95weight percent, or at least 99 weight percent of the thermoplasticcopolyester composition disclosed herein, based on the total weight ofthe second polymeric material. In some instances, the second polymericmaterial includes essentially only one or more disclosed thermoplasticcopolyester compositions. The disclosed methods of manufacturing anarticle comprising a first component and a second component may furthercomprise steps or adjustments as known to the skilled artisan.

In some aspects, the methods of manufacturing an article of footwearinclude injection molding a composition to form a thermoplasticcopolyester foam described herein to produce a foam article or componentof an article, such as an article of footwear. The methods can furthercomprise manufacturing an article or component of an article comprisingproviding a midsole or a component of a midsole, then providing an upperand/or an outsole or outsole component for an article of footwear; andfollowed by combining the midsole or midsole component with the upperand/or the outsole or outsole component to make an article of footwear.In some instances, the method of manufacturing the article of footwearincludes combining an article comprising a thermoplastic copolyesterfoam, an upper, and an outsole to make an article of footwear. Invarious aspects, the upper and/or outsole can comprise the same or adifferent thermoplastic copolyester material, a second polymericmaterial, or combinations thereof. In some instances, the outsole usedin the method can be foamed, partially foamed, or essentially notfoamed. It is understood that a midsole, midsole component, outsole, oroutsole component can be foamed or partially foamed using the methodsdisclosed herein for the preparation of a foam article.

The various disclosed methods can include coupling a first component toa second component. In certain aspects, the disclosed methods compriseforming the first component and second component together. For example,the polymeric material for the first component, i.e., a disclosedthermoplastic copolyester, and the second polymeric material can beadded to a mold sequentially during an injection molding process toprovide a unitary component having a first component, i.e., a foamportion and a second component, i.e., a polymeric layer comprising thesecond polymeric material. In this aspect, a mold can be provided havinga first mold portion having a mold surface. The second polymericmaterial can be added to the mold, so as to form a polymeric layer on atleast a portion of the mold surface. The polymeric material for thefirst component, i.e., a disclosed thermoplastic copolyester, can beinjected into the mold containing the second component, i.e., thepolymeric layer comprising the second polymeric material, and foamedwhile in contact with the polymeric layer. The resultantinjection-molded component is a unitary component, with the secondcomponent, i.e., the polymeric layer, bonded to the first component,i.e., the foam component.

Alternatively or additionally, the second component can be disposed ontothe exterior surface of the first component during a compression moldingstep. For example, a first component can be made such as by injectionmolding, and the foam component can thereafter be compression molded ina mold which includes the second component, and the first componentbonds to the surface of the second component during the compressionmolding process.

The second component can be provided as an already formed component,e.g., a second component, to the injection mold or compression mold. Forexample, the second component, e.g., a film, can be inserted into aninjection mold and held in place against a target surface of the moldvia vacuum ports, electrostatic charge or other method. The secondcomponent may be conformed to the target surface of the mold, forexample, with the application of heat or vacuum before or after it isinserted into the mold. The polymeric material for the first component,i.e., a disclosed thermoplastic copolyester, can then be injected intothe mold containing the film, and foamed as described herein. As aresult the second component becomes an integral part of the moldedcomponent.

Alternatively or additionally, the second component can be disposed ontothe foam component after the foam component has been formed. Accordingto some of the disclosed methods, the second component that is providedseparately from the first component, and are thereafter operably coupledso that the second component is in contact with a targeted portion of anexterior surface of the first component. The second component may becoupled with the exterior surface of a first component using anysuitable method. In an aspect, the second component may be adhesivelylaminated to the first component. In another aspect, the secondcomponent may be coupled with the first component may be thermallylaminated to an exterior surface of the first component. For example,heat may be applied to an exterior surface of the first component, to asurface of the second component, or both, to soften or melt the heatedsurface(s), and the two surfaces may be joined when one or both are inthe softened or melted state. In an aspect, the second component may becoupled with the first component using a flame lamination process.

The second component can be provided as a polymeric coating. Forexample, a polymeric coating can be formed by applying a liquidpolymeric material onto the foam component, such as by spraying, dipcoating, tumble-coating, brushing, or a combination thereof. The liquidpolymeric material can then be dried or cured while in contact with thefirst component.

The polymeric coating can be formed by applying a powered polymericmaterial onto the foam component, such as by spraying, powder-coating,electrostatically coating, tumble-coating, or a combination thereof. Insome aspects, an adhesive could be used to affix the powder to themidsole, and/or a coating can be applied over the powder to hold it inplace on the foam component. Once the powder is affixed to the midsole,it can be left in the form of a powder, or it can be treated so as toform a more uniform coating, such as by heating it to melt it, byapplying a solvent to solubilize it, etc.

Alternatively, the polymeric layer can take the form of a separateelement which is applied to all or a portion of an exterior surface ofthe foam component when incorporating the midsole into an article offootwear. For example, the foam component can be a midsole component ofan article of footwear, and the polymeric layer can be a rand or foxingtape applied around a perimeter of the midsole. The polymeric layer canbe an extension of an outsole covering all or a portion of the bottomsurface of the midsole, and which wraps up and covers at least a portionof the sidewall of the midsole. The polymeric layer can be the “shell”portion of a core-shell sole structure, which covers both the bottomsurface and the sidewalls of the midsole, and which is attached to theupper of the article of footwear.

The foam articles and components can be foamed using any one of themethods described above.

In various aspects, the disclosed methods of manufacturing articlescomprising a first component and a second component, the secondcomponent comprising a second polymer material can produced separatelyvia injection molding with or without the addition of compressed gas,supercritical fluids or other blowing agents upon which the foam articleis produced.

In some instances, the disclosed methods of manufacturing articlescomprising a first component and a second component comprise injectionvia overmolding. In some instances, overmolding can comprise sequentialinjection of a polymeric material for the first component, i.e., adisclosed thermoplastic copolyester, and a second polymeric material inthe same process, or wherein the second material was produced in aseparate process, and subsequently inserted into the mold after whichfoam article from the first material is overmolded. The second componentcan be produced separately via injection molding with only sufficientcompressed gas, supercritical fluids or other blowing agents to achievea density of 0.90 grams per cubic centimeter, 0.85 grams per cubiccentimeter, or 0.80 grams per cubic centimeter.

In some instances, the disclosed methods of manufacturing articlescomprising a first component and a second component comprise a step ofcorona treatment. That is, for example, the second component can be afilm or an outsole or a rand that is pretreated with a plasma or coronatreatment prior to receiving the overmolding assembly described herein.

In some instances, the disclosed methods of manufacturing articlescomprising a first component and a second component comprise a step ofpretreatment with a primer. That is, for example, the second componentcan be a film or an outsole or a rand that is pretreated with a primeralone, or a primer plus and an adhesive prior to receiving theovermolding assembly method described herein.

In some instances, the disclosed methods of manufacturing articlescomprising a first component and a second component comprise a step offused deposition 3D printing. That is, for example, the second componentcan be fused deposition 3D printed onto a first component. In suchinstances, a second polymeric material can be extruded into a fuseddeposition 3D printing filament of about 1.5 mm, about 1.75 mm, about1.85 mm, about 2.85 mm, about 3.0 mm, or other relevant diameter fordeposition and attachment to first component in such a way that itcomprises the ground contact layer, print-on outsole, or other exteriorfeatures. Any grade commonly used in injection molding will typicallysuffice for 3D print filament for fused deposition applications.

The resulting article comprising the first and second components can becharacterized by good bonding strength between the first and the secondcomponents. The ply adhesion strength between the polymeric layer andthe foam component is greater than 2.5 kg force/centimeter or greaterthan 3.0 kg force/centimeter, when determined using the Ply AdhesionTest method described herein. Alternatively additionally, the bondingstrength between the first and the second components can be determinedaccording to the Hand Pull Test, described herein. The disclosedarticles or components can have a bond between the first and the secondcomponents that has an average hand pull test result of greater than orequal to 2.0, or greater than or equal to 2.5, or greater than or equalto 3.0, or greater than or equal to 3.5, or greater than or equal to4.0, or greater than or equal to 4.5, when determined according to theHand Pull Test method described herein.

Each of the first and/or the second components can be characterized byone or more properties. For example, a first and/or a second componentcan have an Akron abrasion of less than 0.50 cubic centimeters lost,optionally less than 0.40 cubic centimeters lost, less than 0.30 cubiccentimeters lost, less than 0.20 cubic centimeters lost, or less than0.10 cubic centimeters lost as determined using the Akron Abrasion Test.The first and/or the second components can have an Akron abrasion ofabout 0.05 cubic centimeters lost, about 0.10 cubic centimeters lost,about 0.15 cubic centimeters lost, about 0.20 cubic centimeters lost,about 0.25 cubic centimeters lost, about 0.30 cubic centimeters lost,about 0.35 cubic centimeters lost, about 0.40 cubic centimeters lost,about 0.45 cubic centimeters lost, or about 0.50 cubic centimeters lostas determined using the Akron Abrasion Test, any range of abrasionvalues encompassed by any of the foregoing values, or any combination ofthe foregoing abrasion values.

The first and/or a second component can have an Akron abrasion of lessthan 500 milligrams lost, optionally less than 400 milligrams lost, lessthan 300 milligrams lost, less than 200 milligrams lost, or less than100 milligrams lost as determined using the Akron Abrasion Test. Thefirst and/or a second component can have an can have an Akron abrasionof about 50 milligrams lost, about 100 milligrams lost, about 150milligrams lost, about 200 milligrams lost, about 250 milligrams lost,about 300 milligrams lost, about 350 milligrams lost, about 400milligrams lost, about 450 milligrams lost, or about 500 milligrams lostas determined using the Akron Abrasion Test, any range of abrasionvalues encompassed by any of the foregoing values, or any combination ofthe foregoing abrasion values.

The first and/or a second component can have a DIN abrasion of less than0.30 cubic centimeters lost, optionally less than 0.20 cubic centimeterslost, less than 0.10 cubic centimeters lost, less than 0.05 cubiccentimeters lost, or less than 0.03 cubic centimeters lost as determinedusing the DIN Abrasion Test. The first and/or a second component canhave a DIN abrasion of about 0.01 cubic centimeters lost, about 0.05cubic centimeters lost, about 0.10 cubic centimeters lost, about 0.15cubic centimeters lost, about 0.20 cubic centimeters lost, about 0.25cubic centimeters lost, or about 0.30 cubic centimeters lost asdetermined using the DIN Abrasion Test, any range of abrasion valuesencompassed by any of the foregoing values, or any combination of theforegoing abrasion values.

The first and/or a second component can have a DIN abrasion of less than300 milligrams lost, optionally less than 250 milligrams lost,optionally less than 200 milligrams lost, optionally less than 150milligrams lost, optionally less than 100 milligrams lost, optionallyless than 80 milligrams lost, optionally less than 50 milligrams lost,or optionally less than 30 milligrams as determined using the DINAbrasion Test. The first and/or a second component can have a DINabrasion of about 10 milligrams lost, about 50 milligrams lost, about100 milligrams lost, about 150 milligrams lost, about 200 milligramslost, about 250 milligrams lost, or about 300 milligrams lost asdetermined using the DIN Abrasion Test, any range of abrasion valuesencompassed by any of the foregoing values, or any combination of theforegoing abrasion values.

The first and/or a second component can described herein whenincorporated into an article the product can have improved tractionproperties. In one aspect, the coefficient of friction of the polymerlayer can be used to measure traction properties.

The first and/or a second component can have a dry dynamic coefficientof friction (COF) on a dry surface (e.g., a smooth, flat, or texturedsurface such as, for example, wooden parquet court, concrete, asphalt,laminate, brick, or ceramic tile) of greater than 0.5, optionally ofgreater than 0.7, greater than 0.8, greater than 0.9, greater than 1.0,as determined using the Dry Outsole Coefficient of Friction Test. Thepolymer layer can have a dry dynamic COF of greater than 0.15,optionally of greater than 0.2, greater than 0.25, or greater than 0.3,using the Dry Upper Coefficient of Friction Test.

The first and/or a second component can have a wet dynamic COF ofgreater than 0.25, optionally of greater than 0.30, greater than 0.35,greater than 0.40, or greater than 0.50, as determined using the WetOutsole Coefficient of Friction Test. The polymer layer can have a wetdynamic COF of greater than 0.15, optionally of greater than 0.2,greater than 0.25, or greater than 0.3, using the Wet Upper Coefficientof Friction Test.

It may be desirable for the dynamic coefficient of friction for the samedry and wet surface (e.g., smooth concrete or court) to be as close aspossible. In one aspect, the difference between the dynamic coefficientof friction of the dry surface and the wet surface is less than 15percent. In another aspect, the difference between the dynamiccoefficient of friction of the dry surface and the wet surface is about0 percent, about 1 percent, about 2 percent, about 3 percent, about 4percent, about 5 percent, about 6 percent, about 7 percent, about 8percent, about 9 percent, about 10 percent, about 11 percent, about 12percent, about 13 percent, about 14 percent, or about 15 percent, anyrange of percentage values encompassed by any of the foregoing values,or any combination of the foregoing percentage values.

The first and/or a second component can have a durometer Shore Ahardness of less than 90 or less than 85 or less than 80. The polymerlayer can have a durometer Shore A hardness of greater than 60 orgreater than 65. The polymer layer can have a durometer Shore A hardnessof about 50 to about 90 Shore A, optionally from about 55 to about 85Shore A, from about 60 to about 80 Shore A, or from about 60 to about 70Shore A. The polymer layer can have a durometer Shore A hardness ofabout 50 A, about 55 A, about 60 A, about 65 A, about 70 A, about 75 A,about 80 A, about 85 A, or about 90 A, any range of Shore A hardnessvalues encompassed by any of the foregoing values, or any combination ofthe foregoing Shore A hardness values.

Thermoplastic Copolyester Composition

The polymeric materials disclosed herein (i.e., the polymeric materialfor the first component of the foam portion and/or the second polymericmaterial) can include or consist essentially of one or morethermoplastic copolyester compositions. In some aspects, a polymericmaterial for the first component includes at least 90 percent or atleast 95 weight percent, or at least 99 weight percent of thethermoplastic copolyester composition disclosed herein, based on thetotal weight of the polymeric material for the first component.

The thermoplastic copolyester compositions include or consistessentially of one or more thermoplastic copolyesters. The disclosedthermoplastic copolyester composition can include at least about 90weight percent or at least about 95 weight percent or at least about 99weight percent of the one or more thermoplastic copolyesters, based onthe total weight of the thermoplastic copolyester composition. In someaspects, the resin component of the thermoplastic copolyestercomposition, which is comprised of all the polymeric materials presentin the thermoplastic copolyester composition, consists essentially ofthe one or more thermoplastic copolyesters. The thermoplasticcopolyesters can include chain units derived from one or more olefinsand chain units derived from one or more ethylenically-unsaturated acidgroups.

The thermoplastic copolyester compositions can have a melt flow index offrom about 5 to about 40, or about 10 to about 20, or about 20 to about30 as determined at 210 degrees C. using a 2.16 kilogram weight.Alternatively or additionally, the thermoplastic copolyestercompositions can have a melt flow index of from about 5 to about 40, orabout 10 about 20, or about 20 to about 30 as determined at 220 degreesC. using a 2.16 kilogram weight. Alternatively or additionally, thethermoplastic copolyester compositions can have a melt flow index offrom about 5 to about 40, or about 10 to about 20, or about 20 to about30 as determined at 230 degrees C. using a 2.16 kilogram weight.

The thermoplastic copolyesters can be terpolymers of moieties derivedfrom ethylene, acrylic acid, and methyl acrylate or butyl acrylate. Insome aspects, a ratio of a total parts by weight of the acrylic acid inthe thermoplastic copolyesters to a total weight of the thermoplasticcopolyesters is about 0.05 to about 0.6, about 0.1 to about 0.6, about0.1 to about 0.5, about 0.15 to about 0.5, or about 0.2 to about 0.5.

The compositions provided herein can include a thermoplastic copolyestercomprising: (a) a plurality of first segments, each first segmentderived from a dihydroxy-terminated polydiol; (b) a plurality of secondsegments, each second segment derived from a diol; and (c) a pluralityof third segments, each third segment derived from an aromaticdicarboxylic acid. In various aspects, the thermoplastic copolyester isa block copolymer. In some aspects, the thermoplastic copolyester is asegmented copolymer. In further aspects, the thermoplastic copolyesteris a random copolymer. In still further aspects, the thermoplasticcopolyester is a condensation copolymer.

The thermoplastic copolyester can have a weight average molecular weightof about 50,000 Daltons to about 1,000,000 Daltons; about 50,000 Daltonsto about 500,000 Daltons; about 75,000 Daltons to about 300,000 Daltons;about 100,000 Daltons to about 250,000 Daltons; about 100,000 Dalton toabout 500,000 Dalton; or a value or values of weight average molecularweight within any of the foregoing ranges or a weight average molecularweight range encompassing any sub-range of the foregoing ranges.

The thermoplastic copolyester can have a ratio of first segments tothird segments from about 1:1 to about 1:5 based on the weight of eachof the first segments and the third segments; about 1:1 to about 1:3based on the weight of each of the first segments and the thirdsegments; about 1:1 to about 1:2 based on the weight of each of thefirst segments and the third segments; about 1:1 to about 1:3 based onthe weight of each of the first segments and the third segments; or avalue or values of have a ratio of first segments to third segmentswithin any of the foregoing ranges or a have a range of ratio of firstsegments to third segments encompassing any sub-range of the foregoingranges.

The thermoplastic copolyester can a ratio of second segments to thirdsegments from about 1:1 to about 1:2 based on the weight of each of thefirst segments and the third segments; about 1:1 to about 1:1.52 basedon the weight of each of the first segments and the third segment; or avalue or values of have a ratio of second segments to third segmentswithin any of the foregoing ranges or a have a range of ratio of secondsegments to third segments encompassing any sub-range of the foregoingranges.

The thermoplastic copolyester can have first segments derived from apoly(alkylene oxide)diol having a number-average molecular weight ofabout 250 Daltons to about 6000 Daltons; about 400 Daltons to about6,000 Daltons; about 350 Daltons to about 5,000 Daltons; about 500Daltons to about 3,000 Daltons; about 2,000 Daltons to about 3,000Daltons; or a value or values of weight average molecular weight withinany of the foregoing ranges or a weight average molecular weight rangeencompassing any sub-range of the foregoing ranges.

The thermoplastic copolyester can have first segments derived from apoly(alkylene oxide)diol such as poly(ethylene ether)diol;poly(propylene ether)diol; poly(tetramethylene ether)diol;poly(pentamethylene ether)diol; poly(hexamethylene ether)diol;poly(heptamethylene ether)diol; poly(octamethylene ether)diol;poly(nonamethylene ether)diol; poly(decamethylene ether)diol; ormixtures thereof. In a still further aspect, the thermoplasticcopolyester can have first segments derived from a poly(alkyleneoxide)diol such as poly(ethylene ether)diol; poly(propylene ether)diol;poly(tetramethylene ether)diol; poly(pentamethylene ether)diol;poly(hexamethylene ether)diol. In a yet further aspect, thethermoplastic copolyester can have first segments derived from apoly(tetramethylene ether)diol.

The thermoplastic copolyester can have second segments derived from adiol having a molecular weight of less than about 250. The diol fromwhich the second segments are derived can be a C2-C8 diol. In a stillfurther aspect, the second segments can be derived from ethanediol;propanediol; butanediol; pentanediol; 2-methyl propanediol; 2,2-dimethylpropanediol; hexanediol; 1,2-dihydroxy cyclohexane; 1,3-dihydroxycyclohexane; 1,4-dihydroxy cyclohexane; and mixtures thereof. In a yetfurther aspect, the second segments can be derived from 1,2-ethanediol,1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and mixtures thereof.In an even further aspect, the second segments can be derived from1,2-ethanediol. In a still further aspect, the second segments can bederived from 1,4-butanediol.

The thermoplastic copolyester can have third segments derived from anaromatic C5-C16 dicarboxylic acid. The aromatic C5-C16 dicarboxylic acidcan have a molecular weight less than about 300 Daltons; about 120Daltons to about 200 Daltons; or a value or values of molecular weightwithin any of the foregoing ranges or a molecular weight rangeencompassing any sub-range of the foregoing ranges. In some instances,the aromatic C5-C16 dicarboxylic acid is terephthalic acid, phthalicacid, isophthalic acid, or a derivative thereof. In a still furtheraspect, the aromatic C5-C16 dicarboxylic acid is a diester derivative ofthe terephthalic acid, phthalic acid, or isophthalic acid. In a yetfurther aspect, the aromatic C5-C16 dicarboxylic acid is terephthalicacid or the dimethyl ester derivative thereof.

The thermoplastic copolyester can comprise: (a) a plurality of firstcopolyester units, each first copolyester unit of the pluralitycomprising the first segment derived from a dihydroxy-terminatedpolydiol and the third segment derived from an aromatic dicarboxylicacid, wherein the first copolyester unit has a structure represented bya Formula 1:

wherein R₁ is a group remaining after removal of terminal hydroxylgroups from the poly(alkylene oxide) diol of the first segment, whereinthe poly(alkylene oxide) diol of the first segment is a poly(alkyleneoxide) diol having a number-average molecular weight of about 400 toabout 6000; and wherein R₂ is a group remaining after removal ofcarboxyl groups from the aromatic dicarboxylic acid of the thirdsegment; and (b) a plurality of second copolyester units, each secondcopolyester unit of the plurality comprising the second segment derivedfrom a diol and the third segment derived from an aromatic dicarboxylicacid, wherein the second copolyester unit has a structure represented bya Formula 2:

wherein R₃ is a group remaining after removal of hydroxyl groups fromthe diol of the second segment derived from a diol, wherein the diol isa diol having a molecular weight of less than about 250; and wherein R₂is the group remaining after removal of carboxyl groups from thearomatic dicarboxylic acid of the third segment.

The thermoplastic copolyester can comprise a plurality of firstcopolyester units having a structure represented by a Formula 3:

wherein R is H or methyl; wherein y is an integer having a value from 1to 10; wherein z is an integer having a value from 2 to 60; and whereina weight average molecular weight of each of the plurality of firstcopolyester units is from about 300 Daltons to about 7,000 Daltons. Insome aspects, in the foregoing formula, y can be is an integer having avalue of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range ofthe foregoing integer values. In some aspects, the foregoing formula, zis an integer having a value from 5 to 60; an integer having a valuefrom 5 to 50; an integer having a value from 5 to 40; an integer havinga value from 4 to 30; an integer having a value from 4 to 20; an integerhaving a value from 2 to 10; or z can be any set or range of theforegoing integer values. In some aspects, R is hydrogen. In a stillfurther aspect, R is methyl. In some instances, R is hydrogen and y isan integer having a value of 1, 2, or 3. Alternatively, in otherinstances, R is methyl and y is an integer having a value of 1.

The thermoplastic copolyester can comprise a plurality of firstcopolyester units having a structure represented by a Formula 4:

wherein z is an integer having a value from 2 to 60; and wherein aweight average molecular weight of each of the plurality of firstcopolyester units is from about 300 Daltons to about 7,000 Daltons. Insome aspects, in the foregoing formula, y can be is an integer having avalue of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range ofthe foregoing integer values. In some aspects, the foregoing formula, zis an integer having a value from 5 to 60; an integer having a valuefrom 5 to 50; an integer having a value from 5 to 40; an integer havinga value from 4 to 30; an integer having a value from 4 to 20; an integerhaving a value from 2 to 10; or z can be any integer value or set ofinteger values within the foregoing ranges or values, or any range ofinteger values encompassing a sub-range the foregoing integer valueranges.

The thermoplastic copolyester can comprise a plurality of firstcopolyester units having a weight average molecular weight from about400 Daltons to about 6,000 Daltons; about 400 Daltons to about 5,000Daltons; about 400 Daltons to about 4,000 Daltons; about 400 Daltons toabout 3,000 Daltons; about 500 Daltons to about 6,000 Daltons; about 500Daltons to about 5,000 Daltons; about 500 Daltons to about 4,000Daltons; about 500 Daltons to about 3,000 Daltons; about 600 Daltons toabout 6,000 Daltons; about 600 Daltons to about 5,000 Daltons; about 600Daltons to about 4,000 Daltons; about 600 Daltons to about 3,000Daltons; about 2,000 Daltons to about 3,000 Daltons; or a value orvalues of weight average molecular weight within any of the foregoingranges or a weight average molecular weight range encompassing anysub-range of the foregoing ranges.

The thermoplastic copolyester can comprise a plurality of secondcopolyester units, each second copolyester unit of the plurality havingrepresented by a Formula 5:

wherein x is an integer having a value from 1 to 20; wherein the foamarticle has a microcellular closed-cell or open-cell foam structure. Insome aspects, in the foregoing formula, x is an integer having a valuefrom 2 to 18; 2 to 17; 2 to 16; 2 to 15; 2 to 14; 2 to 13; 2 to 12; 2 to11; 2 to 10; 2 to 9; 2 to 8; 2 to 7; 2 to 6; 2 to 5; 2 to 4; or x can beany integer value or set of integer values within the foregoing rangesor values, or any range of integer values encompassing a sub-range theforegoing integer value ranges. In a further aspect, x is an integerhaving a value of 2, 3, or 4.

The thermoplastic copolyester can comprise a plurality of secondcopolyester units, each second copolyester unit of the plurality havingrepresented by a Formula 6:

The thermoplastic copolyester can comprise a weight percent range of theplurality of first copolyester units based on total weight of thethermoplastic copolyester such that the weight percent range is about 30weight percent to about 80 weight percent; about 40 weight percent toabout 80 weight percent; about 50 weight percent to about 80 weightpercent; about 30 weight percent to about 70 weight percent; about 40weight percent to about 70 weight percent; about 50 weight percent toabout 70 weight percent; about 40 weight percent to about 65 weightpercent; about 45 weight percent to about 65 weight percent; about 50weight percent to about 65 wt; about 55 weight percent to about 65weight percent; about 40 weight percent to about 60 weight percent;about 45 weight percent to about 60 weight percent; about 50 weightpercent to about 60 weight percent; about 55 weight percent to about 60weight percent; or any weight percent value or set of weight percentvalues within any of the foregoing ranges of weight percent, or anyrange of weight percent values encompassing a sub-set of any of theforegoing ranges.

In some aspects, the thermoplastic copolyester can comprise phaseseparated domains. For example, a plurality of first segments derivedfrom a dihydroxy-terminated polydiol can phase-separate into domainscomprising primarily the first segments. Moreover, a plurality of secondsegments derived from a diol can phase-separate into domains comprisingprimarily the second segments. In other aspects, the thermoplasticcopolyester can comprise phase-separated domains comprising primarily ofa plurality of first copolyester units, each first copolyester unit ofthe plurality comprising the first segment derived from adihydroxy-terminated polydiol and the third segment derived from anaromatic dicarboxylic acid, wherein the first copolyester unit has astructure represented by a Formula 1:

wherein R₁ is a group remaining after removal of terminal hydroxylgroups from the poly(alkylene oxide) diol of the first segment, whereinthe poly(alkylene oxide) diol of the first segment is a poly(alkyleneoxide) diol having a number-average molecular weight of about 400 toabout 6000; and wherein R₂ is a group remaining after removal ofcarboxyl groups from the aromatic dicarboxylic acid of the thirdsegment; and other phase-separated domains comprising primarily of aplurality of second copolyester units, each second copolyester unit ofthe plurality comprising the second segment derived from a diol and thethird segment derived from an aromatic dicarboxylic acid, wherein thesecond copolyester unit has a structure represented by a Formula 2:

wherein R₃ is a group remaining after removal of hydroxyl groups fromthe diol of the second segment derived from a diol, wherein the diol isa diol having a molecular weight of less than about 250; and wherein R₂is the group remaining after removal of carboxyl groups from thearomatic dicarboxylic acid of the third segment.

In other aspects, the thermoplastic copolyester can comprisephase-separated domains comprising primarily of a plurality of firstcopolyester units, each first copolyester unit of the plurality having astructure represented by a Formula 3:

wherein R is H or methyl; wherein y is an integer having a value from 1to 10; wherein z is an integer having a value from 2 to 60; and whereina weight average molecular weight of each of the plurality of firstcopolyester units is from about 300 Daltons to about 7,000 Daltons. Insome aspects, in the foregoing formula, y can be is an integer having avalue of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range ofthe foregoing integer values. In some aspects, the foregoing formula, zis an integer having a value from 5 to 60; an integer having a valuefrom 5 to 50; an integer having a value from 5 to 40; an integer havinga value from 4 to 30; an integer having a value from 4 to 20; an integerhaving a value from 2 to 10; or z can be any set or range of theforegoing integer values. In some aspects, R is hydrogen. In a stillfurther aspect, R is methyl. In some instances, R is hydrogen and y isan integer having a value of 1, 2, or 3. Alternatively, in otherinstances, R is methyl and y is an integer having a value of 1.

In other aspects, the thermoplastic copolyester can comprisephase-separated domains comprising primarily of a plurality of firstcopolyester units, each first copolyester unit of the plurality having astructure represented by a Formula 4:

wherein z is an integer having a value from 2 to 60; and wherein aweight average molecular weight of each of the plurality of firstcopolyester units is from about 300 Daltons to about 7,000 Daltons. Insome aspects, in the foregoing formula, y can be is an integer having avalue of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range ofthe foregoing integer values. In some aspects, the foregoing formula, zis an integer having a value from 5 to 60; an integer having a valuefrom 5 to 50; an integer having a value from 5 to 40; an integer havinga value from 4 to 30; an integer having a value from 4 to 20; an integerhaving a value from 2 to 10; or z can be any integer value or set ofinteger values within the foregoing ranges or values, or any range ofinteger values encompassing a sub-range the foregoing integer valueranges.

The thermoplastic copolyester can comprise phase-separated domainscomprising primarily of a plurality of first copolyester units having aweight average molecular weight from about 400 Daltons to about 6,000Daltons; about 400 Daltons to about 5,000 Daltons; about 400 Daltons toabout 4,000 Daltons; about 400 Daltons to about 3,000 Daltons; about 500Daltons to about 6,000 Daltons; about 500 Daltons to about 5,000Daltons; about 500 Daltons to about 4,000 Daltons; about 500 Daltons toabout 3,000 Daltons; about 600 Daltons to about 6,000 Daltons; about 600Daltons to about 5,000 Daltons; about 600 Daltons to about 4,000Daltons; about 600 Daltons to about 3,000 Daltons; about 2,000 Daltonsto about 3,000 Daltons; or a value or values of weight average molecularweight within any of the foregoing ranges or a weight average molecularweight range encompassing any sub-range of the foregoing ranges.

In other aspects, the thermoplastic copolyester can comprisephase-separated domains comprising a plurality of second copolyesterunits, each second copolyester unit of the plurality having representedby a Formula 5:

wherein x is an integer having a value from 1 to 20; wherein the foamarticle has a microcellular closed-cell or open-cell foam structure. Insome aspects, in the foregoing formula, x is an integer having a valuefrom 2 to 18; 2 to 17; 2 to 16; 2 to 15; 2 to 14; 2 to 13; 2 to 12; 2 to11; 2 to 10; 2 to 9; 2 to 8; 2 to 7; 2 to 6; 2 to 5; 2 to 4; or x can beany integer value or set of integer values within the foregoing rangesor values, or any range of integer values encompassing a sub-range theforegoing integer value ranges. In a further aspect, x is an integerhaving a value of 2, 3, or 4.

In other aspects, the thermoplastic copolyester can comprisephase-separated domains comprising a plurality of second copolyesterunits, each second copolyester unit of the plurality having representedby a Formula 6:

The thermoplastic copolyester can comprise phase-separated domainscomprising a weight percent range of the plurality of first copolyesterunits based on total weight of the thermoplastic copolyester such thatthe weight percent range is about 30 weight percent to about 80 weightpercent; about 40 weight percent to about 80 weight percent; about 50weight percent to about 80 weight percent; about 30 weight percent toabout 70 weight percent; about 40 weight percent to about 70 weightpercent; about 50 weight percent to about 70 weight percent; about 40weight percent to about 65 weight percent; about 45 weight percent toabout 65 weight percent; about 50 weight percent to about 65 wt; about55 weight percent to about 65 weight percent; about 40 weight percent toabout 60 weight percent; about 45 weight percent to about 60 weightpercent; about 50 weight percent to about 60 weight percent; about 55weight percent to about 60 weight percent; or any weight percent valueor set of weight percent values within any of the foregoing ranges ofweight percent, or any range of weight percent values encompassing asub-set of any of the foregoing ranges.

The disclosed thermoplastic copolyester composition, the polymericcomponent of the composition or an individual thermoplastic copolyestercopolymer in neat form can be characterized by one or more properties.In some aspects, the thermoplastic copolyester composition or thepolymeric component, or the polymer has a maximum load of about 10newtons to about 100 newtons, or from about 15 newtons to about 50newtons, or from about 20 newtons to about 40 newtons; or any load valueor set of load values within any of the foregoing ranges of load value,or any range of load values encompassing a sub-set of any of theforegoing ranges, when determined using the Cyclic Tensile Test methoddescribed herein.

The tensile strength of the thermoplastic copolyester composition or ofthe component of the thermoplastic copolyester composition or of athermoplastic copolyester copolymer in neat form is another importantphysical characteristic. The thermoplastic copolyester composition orcomponent or copolymer can have a tensile strength of from 5 kilogramsper square centimeter to 25 kilograms per square centimeter, or of from10 kilograms per square centimeter to 23 kilograms per squarecentimeter, or of from 15 kilograms per square centimeter to 22kilograms per square centimeter; or any load value or set of load valueswithin any of the foregoing ranges of load value, or any range of loadvalues encompassing a sub-set of any of the foregoing ranges, whendetermined using the Cyclic Tensile Test method described herein.

The thermoplastic copolyester composition or polymeric component of thethermoplastic copolyester composition or a thermoplastic copolyestercopolymer in neat form can have a tensile modulus of about 2 megapascalsto about 20 megapascals or from about 5 megapascals to about 15megapascals when determined using the Cyclic Tensile Test methoddescribed herein; or any load value or set of load values within any ofthe foregoing ranges of load value, or any range of load valuesencompassing a sub-set of any of the foregoing ranges.

Exemplary, but non-limiting, thermoplastic polyester elastomers,including thermoplastic copolyesters, that can be used in the disclosedmethods, foams, and articles include “HYTREL” 3078, “HYTREL” 4068, and“HYTREL” 4556 (DuPont, Wilmington, Del., USA); “PELPRENE” P30B, P40B,and P40H (Toyobo U.S.A. Inc., New York, N.Y., USA); “TRIEL” 5300,“TRIEL” 5400, and blends thereof (Samyang Corporation, Korea); “KEYFLEX”BT1028D, BT1033D, BT1035D, BT1040D, BT1045D, and BT1047D (LG Chem,Korea); and “KOPEL” KP3340, KP3346, KP3347, KP3942 (Kolon Plastics,Inc., Korea).

The disclosed thermoplastic copolyester compositions can further includeone or more ionomers, such as any of the “SURLYN” polymers (DuPont,Wilmington, Del., USA). Ionic foams described herein can be made by aprocess/method including receiving a composition described herein, andphysically foaming the composition to form a thermoplastic copolyesterfoam having a density of about 0.7 gram per cubic centimeter or less, or0.5 gram per cubic centimeter or less, or 0.4 gram per cubic centimeteror less, or 0.3 gram per cubic centimeter or less. The process caninclude blowing the composition to produce an article or componentcomprising the thermoplastic copolyester foam. In some examples, theprocess for forming the thermoplastic copolyester foam comprisesinjection molding a mixture including a composition as described hereinand a supercritical fluid (e.g., supercritical carbon dioxide orsupercritical nitrogen) in a mold, and removing the thermoplasticcopolyester foam from the mold.

The disclosed thermoplastic copolyester compositions can further includeone or more thermoplastic polyurethanes, such as “FORTIMO” (MitsuiChemicals, Inc., Tokyo, Japan); “TEXIN” (Covestro LLC, Pittsburgh, Pa.,USA); and “BOUNCELL-X” (Lubrizol Advanced Materials, Inc., Brecksville,Ohio, USA).

The disclosed thermoplastic copolyester compositions can further includeone or more olefinic polymers. Olefinic polymers can includeethylene-based copolymers, propylene-based copolymers, and butene-basedcopolymers. In some aspects, the olefinic polymer is an ethylene-basedcopolymer such as a styrene-ethylene/butylene-styrene (SEBS) copolymer;an ethylene-propylene diene monomer (EPDM) copolymer; an ethylene-vinylacetate (EVA) copolymer; an ethylene alkyl acrylate (EAA) copolymer; anethylene alkyl methacrylate (EAMA) copolymer; any copolymer thereof, andany blend thereof. In some aspects, a ratio V of a total parts by weightof the olefinic polymers present in the composition to a total parts byweight of the thermoplastic copolyesters in the composition is about 0.0to about 0.6, about 0.0 to about 0.4, about 0.01 to about 0.4, or about0.01 to about 0.6, or about 0.1 to about 0.4.

The disclosed thermoplastic copolyester compositions can further includean ethylene-vinyl acetate (EVA) copolymer. The ethylene-vinyl acetate(EVA) copolymer can have a range of vinyl acetate contents, for exampleabout 50 percent to about 90 percent, about 50 percent to about 80percent, about 5 percent to about 50 percent, about 10 percent to about45 percent, about 10 percent to about 30 percent, about 30 percent toabout 45 percent, or about 20 percent to about 35 percent.

Second Polymeric Materials

Having described the foams and methods of forming them, we turn to thesecond polymeric material. According to the various aspects, thedisclosed foam article has a second polymeric material disposed on atleast one exterior surface of the foam. For example, the secondpolymeric material can be a polymeric layer or a polymeric coating or apolymeric film. In some aspects, the second polymeric material has ahigher abrasion resistance than the foam component. The second polymericmaterial may be integral with the foam component, or may be a separatecomponent that is operably coupled with the foam component, as describedherein.

In some aspects, a second polymeric material includes at least 90 weightpercent, or at least 95 weight percent, or at least 99 weight percent ofthe thermoplastic copolyester composition disclosed herein, based on thetotal weight of the second polymeric material. In some instances, thesecond polymeric material includes essentially only one or moredisclosed thermoplastic copolyester compositions.

The second polymeric material can be disposed on at least one exteriorsurface of the foam. For example, where the foam article is a midsole,the second polymeric material can be on all or part of the ground-facing(bottom) surface of the midsole, or on all or part of a side surface ofthe midsole, or any combination thereof.

In certain aspects, the disclosed methods comprise forming the secondpolymeric material integrally with the first component. For example, thepolymeric material for the first component, i.e., a disclosedthermoplastic copolyester, and the second polymeric material can beadded to a mold sequentially during an injection molding process toprovide a unitary component having a foam portion and a second polymericmaterial. In this aspect, a mold can be provided having a first moldportion having a mold surface. The second polymeric material can beadded to the mold, so as to form a layer of second polymeric material onat least a portion of the mold surface. The polymeric material for thefirst component, i.e., a disclosed thermoplastic copolyester, can beinjected into the mold containing the second polymeric material, andfoamed while in contact with the second polymeric material. Theresultant injection-molded component is a unitary component, with thesecond polymeric material bonded to the foam component. Alternatively oradditionally, the second polymeric material can be disposed onto theexterior surface of the foam component during a compression moldingstep. For example, a foam component can be made such as by injectionmolding, and the foam component can thereafter be compression molded ina mold which includes the second polymeric material, and the secondpolymeric material bonds to the surface of the foam during thecompression molding process.

The second polymeric material can be provided as a discrete layer orfilm to the injection mold or compression mold. For example, the layeror film forming the second polymeric material can be inserted into aninjection mold and held in place against a target surface of the moldvia vacuum ports, electrostatic charge or other method. The layer orfilm may be conformed to the target surface of the mold, for example,with the application of heat or vacuum before or after it is insertedinto the mold. The thermoplastic polyester composition can then beinjected into the mold containing the film, and foamed as describedherein. As a result the second polymeric material of the layer or filmbecomes an integral part of the molded component.

Alternatively or additionally, the second polymeric material can bedisposed onto the foam component after the foam component has beenformed. According to some of the disclosed methods, the second polymericmaterial is provided as a layer or film that is provided separately fromthe foam component, and are thereafter operably coupled so that thesecond polymeric material forms a layer on the targeted portion of theexterior surface of the foam. The second polymeric material may becoupled with the exterior surface of a foam component or article usingany suitable method. In an aspect, the second polymeric material may beadhesively laminated to the foam component. In another aspect, thesecond polymeric material may be coupled with the foam component such asby thermally laminating to an exterior surface of the foam. For example,heat may be applied to an exterior surface of the foam component, to asurface of the second polymeric material, or both, to soften or melt therespective heated surface(s), and the two surfaces may be joined whenone or both are in the softened or melted state. In an aspect, thesecond polymeric material may be coupled with the foam component using aflame lamination process.

The second polymeric material can be provided as a polymeric coating.For example, a polymeric coating can be formed by applying a liquidpolymeric material onto the foam component, such as by spraying, dipcoating, tumble-coating, brushing, or a combination thereof. The liquidpolymeric material can then be dried or cured while in contact with themidsole.

The polymeric coating can be formed by applying a powered polymericmaterial onto the foam component, such as by spraying, powder-coating,electrostatically coating, tumble-coating, or a combination thereof. Insome aspects, an adhesive could be used to affix the powder to themidsole, and/or a coating can be applied over the powder to hold it inplace on the foam component. Once the powder is affixed to the midsole,it can be left in the form of a powder, or it can be treated so as toform a more uniform coating, such as by heating it to melt it, byapplying a solvent to solubilize it, etc.

Alternatively, the second polymeric material can take the form of aseparate element which is applied to all or a portion of an exteriorsurface of the foam component when incorporating the midsole into anarticle of footwear. For example, the foam component can be a midsolecomponent of an article of footwear, and the second polymeric materialcan be a rand or foxing tape applied around a perimeter of the midsole.The second polymeric material can be an extension of an outsole coveringall or a portion of the bottom surface of the midsole, and which wrapsup and covers at least a portion of the sidewall of the midsole. Thesecond polymeric material can be the “shell” portion of a core-shellsole structure, which covers both the bottom surface and the sidewallsof the midsole, and which is attached to the upper of the article offootwear.

The resulting article comprising the first component with the secondpolymeric material can be characterized by good bonding strength betweenthe second polymeric material and the foam component. The ply adhesionstrength between the second polymeric material and the foam component isgreater than 2.5 kg force/centimeter or greater than 3.0 kgforce/centimeter, when determined using the Ply Adhesion Test methoddescribed herein.

Second Polymeric Material Properties

The disclosed second polymeric material can be characterized by one ormore properties. In some aspects, the second polymeric material or resinhas a maximum load of about 10 newtons to about 100 newtons, or fromabout 15 newtons to about 50 newtons, or from about 20 newtons to about40 newtons; or any load value or set of load values within any of theforegoing ranges of load value, or any range of load values encompassinga sub-set of any of the foregoing ranges, when determined using theCyclic Tensile Test method described herein.

The tensile strength of the second polymeric material or resin isanother important physical characteristic. The second polymeric materialor resin can have a tensile strength of from 5 kilograms per squarecentimeter to 25 kilograms per square centimeter, or of from 10kilograms per square centimeter to 23 kilograms per square centimeter,or of from 15 kilograms per square centimeter to 22 kilograms per squarecentimeter; or any load value or set of load values within any of theforegoing ranges of load value, or any range of load values encompassinga sub-set of any of the foregoing ranges, when determined using theCyclic Tensile Test method described herein.

The second polymeric material or resin can have a tensile modulus ofabout 2 megapascals to about 20 megapascals or from about 5 megapascalsto about 15 megapascals when determined using the Cyclic Tensile Testmethod described herein; or any load value or set of load values withinany of the foregoing ranges of load value, or any range of load valuesencompassing a sub-set of any of the foregoing ranges.

The second polymeric material can have an Akron abrasion of less than0.50 cubic centimeters lost, optionally less than 0.40 cubic centimeterslost, less than 0.30 cubic centimeters lost, less than 0.20 cubiccentimeters lost, or less than 0.10 cubic centimeters lost as determinedusing the Akron Abrasion Test. The second polymeric material can have anAkron abrasion of about 0.05 cubic centimeters lost, about 0.10 cubiccentimeters lost, about 0.15 cubic centimeters lost, about 0.20 cubiccentimeters lost, about 0.25 cubic centimeters lost, about 0.30 cubiccentimeters lost, about 0.35 cubic centimeters lost, about 0.40 cubiccentimeters lost, about 0.45 cubic centimeters lost, or about 0.50 cubiccentimeters lost as determined using the Akron Abrasion Test, any rangeof abrasion values encompassed by any of the foregoing values, or anycombination of the foregoing abrasion values.

The second polymeric material can have an Akron abrasion of less than500 milligrams lost, optionally less than 400 milligrams lost, less than300 milligrams lost, less than 200 milligrams lost, or less than 100milligrams lost as determined using the Akron Abrasion Test. The secondpolymeric material can have an Akron abrasion of about 50 milligramslost, about 100 milligrams lost, about 150 milligrams lost, about 200milligrams lost, about 250 milligrams lost, about 300 milligrams lost,about 350 milligrams lost, about 400 milligrams lost, about 450milligrams lost, or about 500 milligrams lost as determined using theAkron Abrasion Test, any range of abrasion values encompassed by any ofthe foregoing values, or any combination of the foregoing abrasionvalues.

The second polymeric material can have a DIN abrasion of less than 0.30cubic centimeters lost, optionally less than 0.20 cubic centimeterslost, less than 0.10 cubic centimeters lost, less than 0.05 cubiccentimeters lost, or less than 0.03 cubic centimeters lost as determinedusing the DIN Abrasion Test. The second polymeric material can have aDIN abrasion of about 0.01 cubic centimeters lost, about 0.05 cubiccentimeters lost, about 0.10 cubic centimeters lost, about 0.15 cubiccentimeters lost, about 0.20 cubic centimeters lost, about 0.25 cubiccentimeters lost, or about 0.30 cubic centimeters lost as determinedusing the DIN Abrasion Test, any range of abrasion values encompassed byany of the foregoing values, or any combination of the foregoingabrasion values.

The second polymeric material can have a DIN abrasion of less than 300milligrams lost, optionally less than 250 milligrams lost, optionallyless than 200 milligrams lost, optionally less than 150 milligrams lost,optionally less than 100 milligrams lost, optionally less than 80milligrams lost, optionally less than 50 milligrams lost, or optionallyless than 30 milligrams as determined using the DIN Abrasion Test. Thesecond polymeric material can have a DIN abrasion of about 10 milligramslost, about 50 milligrams lost, about 100 milligrams lost, about 150milligrams lost, about 200 milligrams lost, about 250 milligrams lost,or about 300 milligrams lost as determined using the DIN Abrasion Test,any range of abrasion values encompassed by any of the foregoing values,or any combination of the foregoing abrasion values.

The second polymeric material can have described herein whenincorporated into an article the product has improved tractionproperties. In one aspect, the coefficient of friction of the secondpolymeric material can be used to measure traction properties.

The second polymeric material can have a dry dynamic coefficient offriction (COF) on a dry surface (e.g., a smooth, flat, or texturedsurface such as, for example, wooden parquet court, concrete, asphalt,laminate, brick, or ceramic tile) of greater than 0.5, optionally ofgreater than 0.7, greater than 0.8, greater than 0.9, greater than 1.0,as determined using the Dry Outsole Coefficient of Friction Test. Thesecond polymeric material can have a dry dynamic COF of greater than0.15, optionally of greater than 0.2, greater than 0.25, or greater than0.3, using the Dry Upper Coefficient of Friction Test.

The second polymeric material can have a wet dynamic COF of greater than0.25, optionally of greater than 0.30, greater than 0.35, greater than0.40, or greater than 0.50, as determined using the Wet OutsoleCoefficient of Friction Test. The second polymeric material can have awet dynamic COF of greater than 0.15, optionally of greater than 0.2,greater than 0.25, or greater than 0.3, using the Wet Upper Coefficientof Friction Test.

It may be desirable for the dynamic coefficient of friction for the samedry and wet surface (e.g., smooth concrete or court) to be as close aspossible. In one aspect, the difference between the dynamic coefficientof friction of the dry surface and the wet surface is less than 15percent. In another aspect, the difference between the dynamiccoefficient of friction of the dry surface and the wet surface is about0 percent, about 1 percent, about 2 percent, about 3 percent, about 4percent, about 5 percent, about 6 percent, about 7 percent, about 8percent, about 9 percent, about 10 percent, about 11 percent, about 12percent, about 13 percent, about 14 percent, or about 15 percent, anyrange of percentage values encompassed by any of the foregoing values,or any combination of the foregoing percentage values.

The second polymeric material can have a melting temperature from about100 degrees C. to about 210 degrees C., optionally from about 110degrees C. to about 195 degrees C., from about 120 degrees C. to about180 degrees C., or from about 120 degrees C. to about 170 degrees C. Thesecond polymeric material can have a melting temperature of about 100degrees C., about 115 degrees C., about 120 degrees C., about 125degrees C., about 130 degrees C., about 135 degrees C., about 140degrees C., about 145 degrees C., about 150 degrees C., about 155degrees C., about 160 degrees C., about 165 degrees C., about 170degrees C., about 175 degrees C., about 180 degrees C., about 185degrees C., about 190 degrees C., about 195 degrees C., about 200degrees C., about 205 degrees C., or about 210 degrees C., any range ofmelting or deformation temperature values encompassed by any of theforegoing values, or any combination of the foregoing meltingtemperature values.

The second polymeric material can have a melt flow rate of at least 0.2grams per 10 minutes, optionally at least 5, at least 10, at least 15,at least 20, at least 25, at least 30, at least 40, or at least 50 gramsper 10 minutes, as determined using ASTM D1238-13 at 160 degrees C.using a weight of 2.16 kg. The second polymeric material can have a meltflow rate of at least 0.2 grams per 10 minutes, optionally at least 5,at least 10, at least 15, at least 20, at least 25, at least 30, atleast 40, or at least 50 grams per 10 minutes, as determined using ASTMD1238-13 at 200 degrees C. using a weight of 10 kg.

The second polymeric material can have a melting temperature from about100 degrees C. to about 210 degrees C., optionally from about 110degrees C. to about 195 degrees C., from about 120 degrees C. to about180 degrees C., or from about 120 degrees C. to about 170 degrees C. Thesecond polymeric material can have a melting temperature of about 100degrees C., about 115 degrees C., about 120 degrees C., about 125degrees C., about 130 degrees C., about 135 degrees C., about 140degrees C., about 145 degrees C., about 150 degrees C., about 155degrees C., about 160 degrees C., about 165 degrees C., about 170degrees C., about 175 degrees C., about 180 degrees C., about 185degrees C., about 190 degrees C., about 195 degrees C., about 200degrees C., about 205 degrees C., or about 210 degrees C., any range ofmelting or deformation temperature values encompassed by any of theforegoing values, or any combination of the foregoing meltingtemperature values.

The second polymeric material can have a melt flow index of from about 5to about 40, or about 10 to about 20, or about 20 to about 30 asdetermined at 210 degrees C. using a 2.16 kilogram weight. Alternativelyor additionally, the second polymeric material can have a melt flowindex of from about 5 to about 40, or about 10 about 20, or about 20 toabout 30 as determined at 220 degrees C. using a 2.16 kilogram weight.Alternatively or additionally, the second polymeric material can have amelt flow index of from about 5 to about 40, or about 10 to about 20, orabout 20 to about 30 as determined at 230 degrees C. using a 2.16kilogram weight.

The second polymeric material can have a durometer Shore A hardness ofless than 90 or less than 85 or less than 80. The second polymericmaterial can have a durometer Shore A hardness of greater than 60 orgreater than 65. The second polymeric material can have a durometerShore A hardness of about 50 to about 90 Shore A, optionally from about55 to about 85 Shore A, from about 60 to about 80 Shore A, or from about60 to about 70 Shore A. The second polymeric material can have adurometer Shore A hardness of about 50 A, about 55 A, about 60 A, about65 A, about 70 A, about 75 A, about 80 A, about 85 A, or about 90 A, anyrange of Shore A hardness values encompassed by any of the foregoingvalues, or any combination of the foregoing Shore A hardness values.

The second polymeric material can have a specific gravity from about 0.8to about 1.5, optionally from about 0.85 to about 1.30, or from about0.88 to about 1.20. In another aspect when thermoformed, the firstthermoplastic composition of the film, fibers, filaments, and yarn has aspecific gravity of about 0.8, about 0.85, about 0.9, about 0.95, about1.1, about 1.15, about 1.2, about 1.25, about 1.3, about 1.35, about1.40, about 1.45, or about 1.5, any range of specific gravity valuesencompassed by any of the foregoing values, or any combination of theforegoing specific gravity values.

The second polymeric material can have two or more of the firstproperties, or optionally three or more, four or more, five or more, sixor more, seven or more, or all ten first properties provided above.

In addition to the first properties, the second polymeric material canhave one or more second properties. The second polymeric material canhave a glass transition temperature less than 50 degrees C., optionallyless than 30 degrees C., less than 0 degrees C., less than −10 degreesC., or less than −20 degrees C. The second polymeric material can have astress at break greater than 7 megapascals, optionally greater than 8megapascals, or greater than 8 megapascals as determined using ASTMDE-412 at 25 degrees C. The second polymeric material can have a tensilestress at 300 percent modulus greater than 2 megapascals, optionallygreater than 2.5 megapascals, or greater than 3 megapascals asdetermined using ASTM DE-412 at 25 degrees C. The second polymericmaterial can have an elongation at break greater than 450 percent,optionally greater than 500 percent, or greater than 550 percent asdetermined using ASTM DE-412 at 25 degrees C. The second polymericmaterial can have two or more of the second properties, or optionallythree or more, or all four second properties.

The second polymeric material includes at least one polymer. The secondpolymeric material can be a thermoplastic material. Alternatively, thesecond polymeric material can be a thermoset material. The secondpolymeric material can comprise a thermoplastic elastomer orthermoplastic vulcanizate material for use a type of ground contact,reinforcing skin, containment layer, outsole, rand, or otherapplication.

The second polymeric material can comprise at least one thermoplasticpolyester, including at least one thermoplastic copolyester. The secondpolymeric material can include one or more thermoplastic copolyesters,or can be substantially free of thermoplastic copolyesters. Thethermoplastic copolyester can be any of the thermoplastic copolyestercompositions disclosed herein.

Thermoplastic Elastomers

The second polymeric materials described herein can comprise one or morethermoplastic elastomers. Exemplary thermoplastic elastomers includehomo-polymers and co-polymers. The thermoplastic elastomer can be arandom co-polymer. The thermoplastic elastomer can be a blockco-polymer. The term “polymer” refers to a polymerized molecule havingone or more monomer species, and includes homopolymers and copolymers.The term “copolymer” refers to a polymer having two or more monomerspecies, and includes terpolymers (i.e., copolymers having three monomerspecies). For example, the thermoplastic elastomer can be a blockco-polymer having repeating blocks of polymeric units of the samechemical structure (segments) which are relatively harder (hardsegments), and repeating blocks of polymeric segments which arerelatively softer (soft segments). In various aspects, in blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within the blocksor between the blocks or both within and between the blocks. Particularexamples of hard segments include isocyanate segments and polyamidesegments. Particular examples of soft segments include polyethersegments and polyester segments. As used herein, the polymeric segmentcan be referred to as being a particular type of polymeric segment suchas, for example, an isocyanate segment, a polyamide segment, a polyethersegment, a polyester segment, and the like. It is understood that thechemical structure of the segment is derived from the described chemicalstructure. For example, an isocyanate segment is a polymerized unitincluding an isocyanate functional group. When referring to a block ofpolymeric segments of a particular chemical structure, the block cancontain up to 10 mol percent of segments of other chemical structures.For example, as used herein, a polyether segment is understood toinclude up to 10 mol percent of non-polyether segments.

The thermoplastic elastomer can include one or more of a thermoplasticcopolyester elastomer, a thermoplastic polyether block amide elastomer,a thermoplastic polyurethane elastomer, a polyolefin based-copolymerelastomer, a thermoplastic styrenic copolymer elastomer, a thermoplasticionomer elastomer, or any combination thereof. It should be understoodthat other thermoplastic polymeric materials not specifically describedbelow are also contemplated for use in the coated fiber as describedherein and/or the an uncoated fiber. The thermoplastic elastomer canhave a melting temperature greater than about 110 degrees centigrade andless than about 170 degrees centigrade. The thermoplastic elastomer canhave a melting temperature of about 110 degrees centigrade, about 115degrees centigrade, about 120 degrees centigrade, about 125 degreescentigrade, about 125 degrees centigrade, about 130 degrees centigrade,about 135 degrees centigrade, about 140 degrees centigrade, about 145degrees centigrade, about 150 degrees centigrade, about 155 degreescentigrade, about 160 degrees centigrade, about 165 degrees centigrade,or about 170 degrees centigrade, any range of melting temperature valuesencompassed by any of the foregoing values, or any combination of theforegoing melting temperature values.

The thermoplastic elastomer can have a glass transition temperature(T_(g)) less than 50 degrees C. when determined in accordance with ASTMD3418-97 as described herein below. The thermoplastic elastomer has aglass transition temperature (T_(g)) of about −20 degrees C., about −19degrees C., about −18 degrees C., about −17 degrees C., about −16degrees C., about −15 degrees C., about −14 degrees C., about −13degrees C., about −12 degrees C., about −10 degrees C., about −9 degreesC., about −8 degrees C., about −7 degrees C., about −6 degrees C., about−5 degrees C., about −4 degrees C., about −3 degrees C., about −2degrees C., about −1 degrees C., about 0 degrees C., about 1 degrees C.,about 2 degrees C., about 3 degrees C., about 4 degrees C., about 5degrees C., about 6 degrees C., about 7 degrees C., about 8 degrees C.,about 9 degrees C., about 10 degrees C., about 11 degrees C., about 12degrees C., about 13 degrees C., about 14 degrees C., about 15 degreesC., about 16 degrees C., about 17 degrees C., about 18 degrees C., about19 degrees C., about 20 degrees C., about 21 degrees C., about 22degrees C., about 23 degrees C., about 24 degrees C., about 25 degreesC., about 26 degrees C., about 27 degrees C., about 28 degrees C., about29 degrees C., about 30 degrees C., about 31 degrees C., about 32degrees C., about 33 degrees C., about 34 degrees C., about 35 degreesC., about 36 degrees C., about 37 degrees C., about 38 degrees C., about39 degrees C., about 40 degrees C., about 41 degrees C., about 42degrees C., about 43 degrees C., about 44 degrees C., about 45 degreesC., about 46 degrees C., about 47 degrees C., about 48 degrees C., about49 degrees C., or about 50 degrees C., any range of glass transitiontemperature values encompassed by any of the foregoing values, or anycombination of the foregoing glass transition temperature values, whendetermined in accordance with ASTM D3418-97 as described herein below.

Thermoplastic Polyurethane Elastomers

The thermoplastic elastomer can be a thermoplastic polyurethaneelastomer. The thermoplastic polyurethane elastomer can be athermoplastic block polyurethane co-polymer. The thermoplastic blockpolyurethane co-polymer can be a block copolymer having blocks of hardsegments and blocks of soft segments. The hard segments can comprise orconsist of isocyanate segments. The soft segments can comprise orconsist of polyether segments, or polyester segments, or a combinationof polyether segments and polyester segments. The thermoplastic materialcan comprise or consist essentially of an elastomeric thermoplasticpolyurethane having repeating blocks of hard segments and repeatingblocks of soft segments.

One or more of the thermoplastic polyurethane elastomer can be producedby polymerizing one or more isocyanates with one or more polyols toproduce copolymer chains having carbamate linkages (—N(CO)O—) asillustrated below in Formula 7 below,

where the isocyanate(s) each preferably include two or more isocyanate(—NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups permolecule (although, single-functional isocyanates can also be optionallyincluded, e.g., as chain terminating units). In these aspects, each R₁and R₂ independently is an aliphatic or aromatic segment. Optionally,each R₂ can be a hydrophilic segment.

Unless otherwise indicated, any of the functional groups or chemicalcompounds described herein can be substituted or unsubstituted. A“substituted” group or chemical compound, such as an alkyl, alkenyl,alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxyl, ester,ether, or carboxylic ester refers to an alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxyl, ester, ether, orcarboxylic ester group, has at least one hydrogen radical that issubstituted with a non-hydrogen radical (i.e., a substituent). Examplesof non-hydrogen radicals (or substituents) include, but are not limitedto, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ether, aryl,heteroaryl, heterocycloalkyl, hydroxyl, oxy (or oxo), alkoxyl, ester,thioester, acyl, carboxyl, cyano, nitro, amino, amido, sulfur, and halo.When a substituted alkyl group includes more than one non-hydrogenradical, the substituents can be bound to the same carbon or two or moredifferent carbon atoms.

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates. This can producepolyurethane copolymer chains as illustrated below in Formula 8,

wherein R₃ includes the chain extender. As with each R₁ and R₃, each R₃independently is an aliphatic or aromatic segment.

Each segment R₁, or the first segment, in Formulas 7 and 8 canindependently include a linear or branched C₃₋₃₀ segment, based on theparticular isocyanate(s) used, and can be aliphatic, aromatic, orinclude a combination of aliphatic portions(s) and aromatic portion(s).The term “aliphatic” refers to a saturated or unsaturated organicmolecule that does not include a cyclically conjugated ring systemhaving delocalized pi electrons. In comparison, the term “aromatic”refers to a cyclically conjugated ring system having delocalized pielectrons, which exhibits greater stability than a hypothetical ringsystem having localized pi electrons.

Each segment R₁ can be present in an amount of 5 percent to 85 percentby weight, from 5 percent to 70 percent by weight, or from 10 percent to50 percent by weight, based on the total weight of the reactantmonomers.

In aliphatic aspects (from aliphatic isocyanate(s)), each segment R₁ caninclude a linear aliphatic group, a branched aliphatic group, acycloaliphatic group, or combinations thereof. For instance, eachsegment R₁ can include a linear or branched C₃₋₂₀ alkylene segment(e.g., C₄₋₁₅ alkylene or C₆₋₁₀ alkylene), one or more C₃₋₈cycloalkylenesegments (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, or cyclooctyl), and combinations thereof.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane copolymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

In aromatic aspects (from aromatic isocyanate(s)), each segment R₁ caninclude one or more aromatic groups, such as phenyl, naphthyl,tetrahydronaphthyl, phenanthrenyl, biphenylenyl, indanyl, indenyl,anthracenyl, and fluorenyl. Unless otherwise indicated, an aromaticgroup can be an unsubstituted aromatic group or a substituted aromaticgroup, and can also include heteroaromatic groups. “Heteroaromatic”refers to monocyclic or polycyclic (e.g., fused bicyclic and fusedtricyclic) aromatic ring systems, where one to four ring atoms areselected from oxygen, nitrogen, or sulfur, and the remaining ring atomsare carbon, and where the ring system is joined to the remainder of themolecule by any of the ring atoms. Examples of suitable heteroarylgroups include pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl,imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl,oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl,benzimidazolyl, and benzothiazolyl.

Examples of suitable aromatic diisocyanates for producing thepolyurethane copolymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyl diisocyanate (DBDI),4-chloro-1,3-phenylene diisocyanate, and combinations thereof. In someaspects, the copolymer chains are substantially free of aromatic groups.

The polyurethane copolymer chains can be produced from diisocyanatesincluding HMDI, TDI, MDI, H₁₂ aliphatics, and combinations thereof. Forexample, the coated fiber as described herein of the present disclosurecan comprise one or more polyurethane copolymer chains are produced fromdiisocynates including HMDI, TDI, MDI, H₁₂ aliphatics, and combinationsthereof.

In certain aspects, polyurethane chains which are crosslinked (e.g.,partially crosslinked polyurethane copolymers which retain thermoplasticproperties) or which can be crosslinked, can be used in accordance withthe present disclosure. It is possible to produce crosslinked orcrosslinkable polyurethane copolymer chains using multi-functionalisocyanates. Examples of suitable triisocyanates for producing thepolyurethane copolymer chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

Segment R₃ in Formula 8 can include a linear or branched C₂-C₁₀ segment,based on the particular chain extender polyol used, and can be, forexample, aliphatic, aromatic, or polyether. Examples of suitable chainextender polyols for producing the polyurethane copolymer chains includeethylene glycol, lower oligomers of ethylene glycol (e.g., diethyleneglycol, triethylene glycol, and tetraethylene glycol), 1,2-propyleneglycol, 1,3-propylene glycol, lower oligomers of propylene glycol (e.g.,dipropylene glycol, tripropylene glycol, and tetrapropylene glycol),1,4-butylene glycol, 2,3-butylene glycol, 1,6-hexanediol,1,8-octanediol, neopentyl glycol, 1,4-cyclohexanedimethanol,2-ethyl-1,6-hexanediol, 1-methyl-1,3-propanediol,2-methyl-1,3-propanediol, dihydroxyalkylated aromatic compounds (e.g.,bis(2-hydroxyethyl) ethers of hydroquinone and resorcinol,xylene-α,α-diols, bis(2-hydroxyethyl) ethers of xylene-α,α-diols, andcombinations thereof.

Segment R₂ in Formulas 7 and 8 can include a polyether group, apolyester group, a polycarbonate group, an aliphatic group, or anaromatic group. Each segment R₂ can be present in an amount of 5 percentto 85 percent by weight, from 5 percent to 70 percent by weight, or from10 percent to 50 percent by weight, based on the total weight of thereactant monomers.

Optionally, in some examples, the thermoplastic polyurethane elastomercan be a thermoplastic polyurethane having relatively high degree ofhydrophilicity. For example, the thermoplastic polyurethane can be athermoplastic polyether polyurethane in which segment R₂ in Formulas 7and 8 includes a polyether group, a polyester group, a polycarbonategroup, an aliphatic group, or an aromatic group, wherein the aliphaticgroup or aromatic group is substituted with one or more pendant grouphaving relatively greater degree of hydrophilicity (i.e., relatively“hydrophilic” groups). The relatively “hydrophilic” groups can beselected from the group consisting of hydroxyl, polyether, polyester,polylactone (e.g., polyvinylpyrrolidone (PVP)), amino, carboxylate,sulfonate, phosphate, ammonium (e.g., tertiary and quaternary ammonium),zwitterion (e.g., a betaine, such as poly(carboxybetaine (pCB) andammonium phosphonates such as phosphatidylcholine), and combinationsthereof. In such examples, this relatively hydrophilic group or segmentof R₂ can form portions of the polyurethane backbone, or can be graftedto the polyurethane backbone as a pendant group. In some examples, thependant hydrophilic group or segment can be bonded to the aliphaticgroup or aromatic group through a linker. Each segment R₂ can be presentin an amount of 5 percent to 85 percent by weight, from 5 percent to 70percent by weight, or from 10 percent to 50 percent by weight, based onthe total weight of the reactant monomers.

In some examples, at least one R₂ segment of the thermoplasticpolyurethane elastomer includes a polyether segment (i.e., a segmenthaving one or more ether groups). Suitable polyethers include, but arenot limited to polyethylene oxide (PEO), polypropylene oxide (PPO),polytetrahydrofuran (PTHF), polytetramethylene oxide (PT_(m)O), andcombinations thereof. The term “alkyl” as used herein refers to straightchained and branched saturated hydrocarbon groups containing one tothirty carbon atoms, for example, one to twenty carbon atoms, or one toten carbon atoms. The term C_(n) means the alkyl group has “n” carbonatoms. For example, C₄ alkyl refers to an alkyl group that has 4 carbonatoms. C₁₋₇ alkyl refers to an alkyl group having a number of carbonatoms encompassing the entire range (i.e., 1 to 7 carbon atoms), as wellas all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7carbon atoms). Non-limiting examples of alkyl groups include, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl(1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unlessotherwise indicated, an alkyl group can be an unsubstituted alkyl groupor a substituted alkyl group.

In some examples of the thermoplastic polyurethane elastomer, the atleast one R₂ segment includes a polyester segment. The polyester segmentcan be derived from the polyesterification of one or more dihydricalcohols (e.g., ethylene glycol, 1,3-propylene glycol, 1,2-propyleneglycol, 1,4-butanediol, 1,3-butanediol,2-methylpentanediol-1,5,diethylene glycol, 1,5-pentanediol,1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, andcombinations thereof) with one or more dicarboxylic acids (e.g., adipicacid, succinic acid, sebacic acid, suberic acid, methyladipic acid,glutaric acid, pimelic acid, azelaic acid, thiodipropionic acid andcitraconic acid and combinations thereof). The polyester also can bederived from polycarbonate prepolymers, such as poly(hexamethylenecarbonate) glycol, poly(propylene carbonate) glycol, poly(tetramethylenecarbonate)glycol, and poly(nonanemethylene carbonate) glycol. Suitablepolyesters can include, for example, polyethylene adipate (PEA),poly(1,4-butylene adipate), poly(tetramethylene adipate),poly(hexamethylene adipate), polycaprolactone, polyhexamethylenecarbonate, poly(propylene carbonate), poly(tetramethylene carbonate),poly(nonanemethylene carbonate), and combinations thereof.

In various of the thermoplastic polyurethane elastomer, at least one R₂segment includes a polycarbonate segment. The polycarbonate segment canbe derived from the reaction of one or more dihydric alcohols (e.g.,ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,1,4-butanediol, 1,3-butanediol, 2-methylpentanediol-1,5, diethyleneglycol, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with ethylenecarbonate.

In various examples of the thermoplastic polyurethane elastomer, atleast one R₂ segment can include an aliphatic group substituted with oneor more groups having a relatively greater degree of hydrophilicity,i.e., a relatively “hydrophilic” group. The one or more relativelyhydrophilic group can be selected from the group consisting of hydroxyl,polyether, polyester, polylactone (e.g., polyvinylpyrrolidone), amino,carboxylate, sulfonate, phosphate, ammonium (e.g., tertiary andquaternary ammonium), zwitterion (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonates such asphosphatidylcholine), and combinations thereof. In some examples, thealiphatic group is linear and can include, for example, a C₁₋₂₀ alkylenechain or a C₁₋₂₀ alkenylene chain (e.g., methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, ethenylene, propenylene,butenylene, pentenylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). Theterm “alkylene” refers to a bivalent hydrocarbon. The term C_(n) meansthe alkylene group has “n” carbon atoms. For example, C₁₋₆ alkylenerefers to an alkylene group having, e.g., 1, 2, 3, 4, 5, or 6 carbonatoms. The term “alkenylene” refers to a bivalent hydrocarbon having atleast one double bond.

In some cases, at least one R₂ segment includes an aromatic groupsubstituted with one or more relatively hydrophilic group. The one ormore hydrophilic group can be selected from the group consisting ofhydroxyl, polyether, polyester, polylactone (e.g.,polyvinylpyrrolidone), amino, carboxylate, sulfonate, phosphate,ammonium (e.g., tertiary and quaternary ammonium), zwitterionic (e.g., abetaine, such as poly(carboxybetaine (pCB) and ammonium phosphonategroups such as phosphatidylcholine), and combinations thereof. Suitablearomatic groups include, but are not limited to, phenyl, naphthyl,tetrahydronaphthyl, phenanthrenyl, biphenylenyl, indanyl, indenyl,anthracenyl, fluorenylpyridyl, pyrazinyl, pyrimidinyl, pyrrolyl,pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isooxazolyl,thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl,benzoxazolyl, benzimidazolyl, and benzothiazolyl groups, andcombinations thereof.

The aliphatic and aromatic groups can be substituted with one or morependant relatively hydrophilic and/or charged groups. The pendanthydrophilic group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9,10 or more) hydroxyl groups. The pendant hydrophilic group includes oneor more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, thealiphatic group can include one or more polyacrylic acid group. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, thependant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7,8, 9, 10 or more) phosphate groups. In some examples, the pendanthydrophilic group includes one or more ammonium groups (e.g., tertiaryand/or quaternary ammonium). In other examples, the pendant hydrophilicgroup includes one or more zwitterionic groups (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonate groups such as aphosphatidylcholine group).

The R₂ segment can include charged groups that are capable of binding toa counterion to ionically crosslink the thermoplastic elastomer and formionomers. In these aspects, for example, R₂ is an aliphatic or aromaticgroup having pendant amino, carboxylate, sulfonate, phosphate, ammonium,or zwitterionic groups, or combinations thereof.

In various cases when a pendant hydrophilic group is present, thependant “hydrophilic” group is at least one polyether group, such as twopolyether groups. In other cases, the pendant hydrophilic group is atleast one polyester. In various cases, the pendant hydrophilic group ispolylactone group (e.g., polyvinylpyrrolidone). Each carbon atom of thependant hydrophilic group can optionally be substituted with, e.g., aC₁₋₆ alkyl group. In some of these aspects, the aliphatic and aromaticgroups can be graft polymeric groups, wherein the pendant groups arehomopolymeric groups (e.g., polyether groups, polyester groups,polyvinylpyrrolidone groups).

The pendant hydrophilic group can be a polyether group (e.g., apolyethylene oxide group, a polyethylene glycol group), apolyvinylpyrrolidone group, a polyacrylic acid group, or combinationsthereof.

The pendant hydrophilic group can be bonded to the aliphatic group oraromatic group through a linker. The linker can be any bifunctionalsmall molecule (e.g., C₁₋₂₀) capable of linking the pendant hydrophilicgroup to the aliphatic or aromatic group. For example, the linker caninclude a diisocyanate group, as previously described herein, which whenlinked to the pendant hydrophilic group and to the aliphatic or aromaticgroup forms a carbamate bond. The linker can be 4,4′-diphenylmethanediisocyanate (MDI), as shown below in Formula 9,

The pendant hydrophilic group can be a polyethylene oxide group and thelinking group is MDI, as shown below in Formula 10,

The pendant hydrophilic group can be functionalized to enable it to bondto the aliphatic or aromatic group, optionally through the linker. Invarious aspects, for example, when the pendant hydrophilic groupincludes an alkene group, which can undergo a Michael addition with asulfhydryl-containing bifunctional molecule (i.e., a molecule having asecond reactive group, such as a hydroxyl group or amino group), toresult in a hydrophilic group that can react with the polymer backbone,optionally through the linker, using the second reactive group. Forexample, when the pendant hydrophilic group is a polyvinylpyrrolidonegroup, it can react with the sulfhydryl group on mercaptoethanol toresult in hydroxyl-functionalized polyvinylpyrrolidone, as shown belowin Formula 11,

In some of the aspects disclosed herein, at least one R₂ segmentincludes a polytetramethylene oxide group. In other exemplary aspects,at least one R₂ segment can include an aliphatic polyol groupfunctionalized with a polyethylene oxide group or polyvinylpyrrolidonegroup, such as the polyols described in E.P. Patent No. 2 462 908. Forexample, the R₂ segment can be derived from the reaction product of apolyol (e.g., pentaerythritol or 2,2,3-trihydroxypropanol) and eitherMDI-derivatized methoxypolyethylene glycol (to obtain compounds as shownin Formulas 12 or 13) or with MDI-derivatized polyvinylpyrrolidone (toobtain compounds as shown in Formulas 14 or 15) that had been previouslybeen reacted with mercaptoethanol, as shown below.

In various cases, at least one R₂ is a polysiloxane, In these cases, R₂can be derived from a silicone monomer of Formula 16, such as a siliconemonomer disclosed in U.S. Pat. No. 5,969,076, which is herebyincorporated by reference:

wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or10); each R₄ independently is hydrogen, C₁₋₁₈ alkyl, C₂₋₁₈ alkenyl,aryl, or polyether; and each R₅ independently is C₁₋₁₀ alkylene,polyether, or polyurethane.

Each R₄ can independently be a H, C₁₋₁₀ alkyl, C₂₋₁₀ alkenyl, C₁₋₆ aryl,polyethylene, polypropylene, or polybutylene group. For example, each R₄can independently be selected from the group consisting of methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl,ethenyl, propenyl, phenyl, and polyethylene groups.

Each R⁵ can independently include a C₁₋₁₀ alkylene group (e.g., amethylene, ethylene, propylene, butylene, pentylene, hexylene,heptylene, octylene, nonylene, or decylene group). In other cases, eachR⁵ is a polyether group (e.g., a polyethylene, polypropylene, orpolybutylene group). In various cases, each R⁵ is a polyurethane group.

Optionally, the thermoplastic polyurethane elastomer can include an atleast partially crosslinked polymeric network that includes copolymerchains that are derivatives of polyurethane. In such cases, it isunderstood that the level of crosslinking is such that the polyurethaneretains thermoplastic properties (i.e., the crosslinked thermoplasticpolyurethane can be softened or melted and re-solidified under theprocessing conditions described herein). This crosslinked polymericnetwork can be produced by polymerizing one or more isocyanates with oneor more polyamino compounds, polysulfhydryl compounds, or combinationsthereof, as shown in Formulas 17 and 18, below:

wherein the variables are as described above. Additionally, theisocyanates can also be chain extended with one or more polyamino orpolythiol chain extenders to bridge two or more isocyanates, such aspreviously described for the polyurethanes of Formula 2.

The thermoplastic polyurethane elastomer can be composed of MDI,TP_(m)O, and 1,4-butylene glycol, as described in U.S. Pat. No.4,523,005. For example, the second polymeric material as describedherein can comprise a thermoplastic polyurethane elastomer composed ofMDI, P T_(m)O, and 1,4-butylene glycol.

As described herein, the thermoplastic polyurethane elastomer can bephysically crosslinked through e.g., nonpolar or polar interactionsbetween the urethane or carbamate groups on the polymers (the hardsegments. In these aspects, component R₁ in Formula 1, and components R₁and R₃ in Formula 2, forms the portion of the polymer often referred toas the “hard segment”, and component R₂ forms the portion of the polymeroften referred to as the “soft segment”. In these aspects, the softsegment can be covalently bonded to the hard segment. In some examples,the thermoplastic polyurethane elastomer having physically crosslinkedhard and soft segments can be a hydrophilic thermoplastic polyurethaneelastomer (i.e., a thermoplastic polyurethane elastomer includinghydrophilic groups as disclosed herein).

Commercially available thermoplastic polyurethane elastomers havinggreater hydrophilicity suitable for the present use include, but are notlimited to those under the tradename “TECOPHILIC”, such as TG-500,TG-2000, SP-80A-150, SP-93A-100, SP-60D-60 (Lubrizol, Countryside,Ill.), “ESTANE” (e.g., 58238, T470A-, 2350-75A-030; Lubrizol,Countryside, Ill.), and “ELASTOLLAN” (e.g., 9500, B70A; BASF).

The thermoplastic polyurethane elastomer can be partially covalentlycrosslinked, as previously described herein.

The second polymeric material can include one or more thermoplasticpolyurethanes (TPUs), such as “FORTIMO” (Mitsui Chemicals, Inc., Tokyo,Japan); “TEXIN” (Covestro LLC, Pittsburgh, Pa., USA); and “BOUNCELL-X”(Lubrizol Advanced Materials, Inc., Brecksville, Ohio, USA). The polymercomponent of second polymeric material (i.e., the component consistingof all the polymers present in the second polymeric material) cancomprise at least 80 weight percent of TPUs, or at least 90 weightpercent of TPUs, or at least 95 weight percent of TPUs, based on a totalweight of the second polymeric material. The second polymeric materialcan include one or more thermoplastic polyurethane hot-melt adhesives,such as, for example, “NASA-T” hot-melt film (Sambu Fine Chemicals,Gimhae-si, Gyeongsangdam-do, Korea).

Thermoplastic Block Co-Polyamide Elastomers

In various aspects, the second polymeric material as described hereincan comprise one or more thermoplastic elastomers comprising athermoplastic block co-polyamide elastomer. The thermoplastic blockco-polyamide can comprise a number of polyamide segments havingdifferent polyamide chemical structures (e.g., polyamide 6 segments,polyamide 11 segments, polyamide 12 segments, polyamide 66 segments,etc.). The polyamide segments having different chemical structure can bearranged randomly, or can be arranged as repeating blocks.

The block co-polyamide can have repeating blocks of hard segments, andrepeating blocks soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thethermoplastic elastomer can be an elastomeric thermoplastic co-polyamidecomprising or consisting of block co-polyamides having repeating blocksof hard segments and repeating blocks of soft segments. In blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within the blocksor between the blocks or both within and between the blocks.

The polyamide segments of the block co-polyamide can comprise or consistof polyamide 6 segments, polyamide 11 segments, polyamide 12 segments,polyamide 66 segments, or any combination thereof. The polyamidesegments of the co-polyamide can be arranged randomly, or can bearranged as repeating blocks. In a particular example, the polyamidesegments can comprise or consist of polyamide 6 segments, or polyamide12 segments, or both polyamide 6 segment and polyamide 12 segments. Inthe example where the polyamide segments of the co-polyamide include ofpolyamide 6 segments and polyamide 12 segments, the segments can bearranged randomly. The non-polyamide segments of the co-polyamide cancomprise or consist of polyether segments, polyester segments, or bothpolyether segments and polyester segments. The co-polyamide can be ablock co-polyamide, or can be a random co-polyamide. The thermoplasticcopolyamide can be formed from the polycodensation of a polyamideoligomer or prepolymer with a second oligomer prepolymer to form a blockcopolyamide (i.e., a block co-polymer including polyamide segments.Optionally, the second prepolymer can be a hydrophilic prepolymer.

The thermoplastic polyamide itself, or the polyamide segment of thethermoplastic copolyamide can be derived from the condensation ofpolyamide prepolymers, such as lactams, amino acids, and/or diaminocompounds with dicarboxylic acids, or activated forms thereof. Theresulting polyamide segments include amide linkages (—(CO)NH—). The term“amino acid” refers to a molecule having at least one amino group and atleast one carboxyl group. Each polyamide segment of the thermoplasticpolyamide can be the same or different.

The thermoplastic polyamide or the polyamide segment of thethermoplastic copolyamide is derived from the polycondensation oflactams and/or amino acids, and includes an amide segment having astructure shown in Formula 19, below, wherein R₆ is the segment of thepolyamide derived from the lactam or amino acid.

In some aspects, R₆ is derived from a lactam. In some cases, R₆ isderived from a C₃₋₂₀ lactam, or a C₄₋₁₅ lactam, or a C₆₋₁₂ lactam. Forexample, R₆ can be derived from caprolactam or laurolactam. In somecases, R₆ is derived from one or more amino acids. In various cases, R₆is derived from a C₄₋₂₅ amino acid, or a C₅₋₂₀ amino acid, or a C₈₋₁₅amino acid. For example, R₆ can be derived from 12-aminolauric acid or11-aminoundecanoic acid.

Optionally, in order to increase the relative degree of hydrophilicityof the thermoplastic copolyamide, Formula 20 can include apolyamide-polyether block copolymer segment, as shown below:

wherein m is 3-20, and n is 1-8. In some exemplary aspects, m is 4-15,or 6-12 (e.g., 6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. Forexample, m can be 11 or 12, and n can be 1 or 3. The thermoplasticpolyamide or the polyamide segment of the thermoplastic co-polyamide canbe derived from the condensation of diamino compounds with dicarboxylicacids, or activated forms thereof, and includes an amide segment havinga structure shown in Formula 21, below, wherein R₇ is the segment of thepolyamide derived from the diamino compound, R₈ is the segment derivedfrom the dicarboxylic acid compound:

In some aspects, R₇ is derived from a diamino compound that includes analiphatic group having C₄₋₁₅ carbon atoms, or C₅₋₁₀ carbon atoms, orC₆₋₉ carbon atoms. The diamino compound can include an aromatic group,such as phenyl, naphthyl, xylyl, and tolyl. Suitable diamino compoundsfrom which R₇ can be derived include, but are not limited to,hexamethylene diamine (HMD), tetramethylene diamine, trimethylhexamethylene diamine (THMD), m-xylylene diamine (MXD), and1,5-pentamine diamine. R₈ can be derived from a dicarboxylic acid oractivated form thereof, includes an aliphatic group having C₄₋₁₅ carbonatoms, or C₅₋₁₂ carbon atoms, or C₆₋₁₀ carbon atoms. The dicarboxylicacid or activated form thereof from which R₈ can be derived can includean aromatic group, such as phenyl, naphthyl, xylyl, and tolyl groups.Suitable carboxylic acids or activated forms thereof from which R₈ canbe derived include, but are not limited to adipic acid, sebacic acid,terephthalic acid, and isophthalic acid. The copolymer chains can besubstantially free of aromatic groups.

Each polyamide segment of the thermoplastic polyamide (including thethermoplastic copolyamide) can independently be derived from a polyamideprepolymer selected from the group consisting of 12-aminolauric acid,caprolactam, hexamethylene diamine and adipic acid.

The thermoplastic polyamide can comprise or consist of a thermoplasticpoly(ether-block-amide). The thermoplastic poly(ether-block-amide) canbe formed from the polycondensation of a carboxylic acid terminatedpolyamide prepolymer and a hydroxyl terminated polyether prepolymer toform a thermoplastic poly(ether-block-amide), as shown in Formula 22:

A disclosed poly(ether block amide) polymer can be prepared bypolycondensation of polyamide blocks containing reactive ends withpolyether blocks containing reactive ends. Examples include, but are notlimited to: 1) polyamide blocks containing diamine chain ends withpolyoxyalkylene blocks containing carboxylic chain ends; 2) polyamideblocks containing dicarboxylic chain ends with polyoxyalkylene blockscontaining diamine chain ends obtained by cyanoethylation andhydrogenation of aliphatic dihydroxylated alpha-omega polyoxyalkylenesknown as polyether diols; 3) polyamide blocks containing dicarboxylicchain ends with polyether diols, the products obtained in thisparticular case being polyetheresteramides. The polyamide block of thethermoplastic poly(ether-block-amide) can be derived from lactams, aminoacids, and/or diamino compounds with dicarboxylic acids as previouslydescribed. The polyether block can be derived from one or morepolyethers selected from the group consisting of polyethylene oxide(PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof.

Poly(ether block amide) polymers include those comprising polyamideblocks comprising dicarboxylic chain ends derived from the condensationof α, ω-aminocarboxylic acids, of lactams or of dicarboxylic acids anddiamines in the presence of a chain-limiting dicarboxylic acid. Inpoly(ether block amide) polymers of this type, a α, ω-aminocarboxylicacid such as aminoundecanoic acid can be used; a lactam such ascaprolactam or lauryllactam can be used; a dicarboxylic acid such asadipic acid, decanedioic acid or dodecanedioic acid can be used; and adiamine such as hexamethylenediamine can be used; or variouscombinations of any of the foregoing. The copolymer can comprisepolyamide blocks comprising polyamide 12 or of polyamide 6.

Poly(ether block amide) polymers include those comprising polyamideblocks derived from the condensation of one or more α, ω-aminocarboxylicacids and/or of one or more lactams containing from 6 to 12 carbon atomsin the presence of a dicarboxylic acid containing from 4 to 12 carbonatoms, and are of low mass, i.e., they have an M_(n) of from 400 to1000. In poly(ether block amide) polymers of this type, a α,ω-aminocarboxylic acid such as aminoundecanoic acid or aminododecanoicacid can be used; a dicarboxylic acids such as adipic acid, sebacicacid, isophthalic acid, butanedioic acid, 1,4-cyclohexyldicarboxylicacid, terephthalic acid, the sodium or lithium salt of sulphoisophthalicacid, dimerized fatty acids (these dimerized fatty acids have a dimercontent of at least 98% percent and are preferably hydrogenated) anddodecanedioic acid HOOC—(CH₂)₁₀—COOH can be used; and a lactam such ascaprolactam and lauryllactam can be used; or various combinations of anyof the foregoing. The copolymer can comprise polyamide blocks obtainedby condensation of lauryllactam in the presence of adipic acid ordodecanedioic acid and with a M_(n) of 750 have a melting point of127-130 degrees centigrade. The various constituents of the polyamideblock and their proportion can be chosen in order to obtain a meltingpoint of less than 150 degrees centigrade. and advantageously between 90degrees centigrade and 135 degrees centigrade.

Poly(ether block amide) polymers include those comprising polyamideblocks derived from the condensation of at least one α,ω-aminocarboxylic acid (or a lactam), at least one diamine and at leastone dicarboxylic acid. In copolymers of this type, a α,ω-aminocarboxylicacid, the lactam and the dicarboxylic acid can be chosen from thosedescribed herein above and the diamine such as an aliphatic diaminecontaining from 6 to 12 atoms and can be arylic and/or saturated cyclicsuch as, but not limited to, hexamethylenediamine, piperazine,1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylenediamine,octamethylene-diamine, decamethylenediamine, dodecamethylenediamine,1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols,isophoronediamine (IPD), methylpentamethylenediamine (MPDM),bis(aminocyclohexyl)methane (BACM) andbis(3-methyl-4-aminocyclohexyl)methane (BMACM) can be used.

The constituents of the polyamide block and their proportion can bechosen in order to obtain a melting point of less than 150 degreescentigrade and advantageously between 90 degrees centigrade and 135degrees centigrade. The various constituents of the polyamide block andtheir proportion can be chosen in order to obtain a melting point ofless than 150 degrees centigrade and advantageously between 90 degreescentigrade and 135 degrees centigrade.

The number average molar mass of the polyamide blocks can be from about300 g/mol and about 15,000 g/mol, from about 500 g/mol and about 10,000g/mol, from about 500 g/mol and about 6,000 g/mol, from about 500 g/molto 5,000 g/mol, and from about 600 g/mol and about 5,000 g/mol. Thenumber average molecular weight of the polyether block can range fromabout 100 g/mol to about 6,000 g/mol, from about 400 g/mol to 3000 g/moland from about 200 g/mol to about 3,000 g/mol. The polyether (PE)content (x) of the poly(ether block amide) polymer can be from about0.05 to about 0.8 (i.e., from about 5 mol percent to about 80 molpercent). The polyether blocks can be present from about 10 wt percentto about 50 wt percent, from about 20 wt percent to about 40 wt percent,and from about 30 wt percent to about 40 wt percent. The polyamideblocks can be present from about 50 wt percent to about 90 wt percent,from about 60 wt percent to about 80 wt percent, and from about 70 wtpercent to about 90 wt percent.

The polyether blocks can contain units other than ethylene oxide units,such as, for example, propylene oxide or polytetrahydrofuran (whichleads to polytetramethylene glycol sequences). It is also possible touse simultaneously PEG blocks, i.e. those consisting of ethylene oxideunits, PPG blocks, i.e. those consisting of propylene oxide units, andPTMG blocks, i.e. those consisting of tetramethylene glycol units, alsoknown as polytetrahydrofuran. PPG or PTMG blocks are advantageouslyused. The amount of polyether blocks in these copolymers containingpolyamide and polyether blocks can be from about 10 wt percent to about50 wt percent of the copolymer and from about 35 wt percent to about 50wt percent.

The copolymers containing polyamide blocks and polyether blocks can beprepared by any means for attaching the polyamide blocks and thepolyether blocks. In practice, two processes are essentially used, onebeing a 2-step process and the other a one-step process.

In the two-step process, the polyamide blocks having dicarboxylic chainends are prepared first, and then, in a second step, these polyamideblocks are linked to the polyether blocks. The polyamide blocks havingdicarboxylic chain ends are derived from the condensation of polyamideprecursors in the presence of a chain-stopper dicarboxylic acid. If thepolyamide precursors are only lactams or α,ω-aminocarboxylic acids, adicarboxylic acid is added. If the precursors already comprise adicarboxylic acid, this is used in excess with respect to thestoichiometry of the diamines. The reaction usually takes place between180 and 300 degrees centigrade, preferably 200 to 290 degreescentigrade, and the pressure in the reactor is set between 5 and 30 barand maintained for approximately 2 to 3 hours. The pressure in thereactor is slowly reduced to a T_(m)ospheric pressure and then theexcess water is distilled off, for example for one or two hours.

Once the polyamide having carboxylic acid end groups has been prepared,the polyether, the polyol and a catalyst are then added. The totalamount of polyether can be divided and added in one or more portions, ascan the catalyst. The polyether can be added first and the reaction ofthe OH end groups of the polyether and of the polyol with the COOH endgroups of the polyamide starts, with the formation of ester linkages andthe elimination of water. Water is removed as much as possible from thereaction mixture by distillation and then the catalyst is introduced inorder to complete the linking of the polyamide blocks to the polyetherblocks. This second step takes place with stirring, preferably under avacuum of at least 50 mbar (5000 Pa) at a temperature such that thereactants and the copolymers obtained are in the molten state. By way ofexample, this temperature can be between 100 and 400 degrees centigradeand usually between 200 and 250 degrees centigrade. The reaction ismonitored by measuring the torque exerted by the polymer melt on thestirrer or by measuring the electric power consumed by the stirrer. Theend of the reaction is determined by the value of the torque or of thetarget power. The catalyst is defined as being any product whichpromotes the linking of the polyamide blocks to the polyether blocks byesterification. Advantageously, the catalyst is a derivative of a metal(M) chosen from the group formed by titanium, zirconium and hafnium.

The derivative can be prepared from a tetraalkoxides consistent with thegeneral formula M(OR)₄, in which M represents titanium, zirconium orhafnium and R, which can be identical or different, represents linear orbranched alkyl radicals having from 1 to 24 carbon atoms.

The catalyst can comprise a salt of the metal (M), particularly the saltof (M) and of an organic acid and the complex salts of the oxide of (M)and/or the hydroxide of (M) and an organic acid. The organic acid can beformic acid, acetic acid, propionic acid, butyric acid, valeric acid,caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid,cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, maleic acid, fumaric acid, phthalic acid and crotonic acid. Aceticand propionic acids are particularly preferred. M can be zirconium andsuch salts are called zirconyl salts, e.g., the commercially availableproduct sold under the name zirconyl acetate.

The weight proportion of catalyst can vary from about 0.01 to about 5percent of the weight of the mixture of the dicarboxylic polyamide withthe polyetherdiol and the polyol. The weight proportion of catalyst canvary from about 0.05 to about 2 percent of the weight of the mixture ofthe dicarboxylic polyamide with the polyetherdiol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper andthe polyether are blended together; what is then obtained is a polymerhaving essentially polyether blocks and polyamide blocks of veryvariable length, but also the various reactants that have reactedrandomly, which are distributed randomly along the polymer chain. Theyare the same reactants and the same catalyst as in the two-step processdescribed above. If the polyamide precursors are only lactams, it isadvantageous to add a little water. The copolymer has essentially thesame polyether blocks and the same polyamide blocks, but also a smallportion of the various reactants that have reacted randomly, which aredistributed randomly along the polymer chain. As in the first step ofthe two-step process described above, the reactor is closed and heated,with stirring. The pressure established is between 5 and 30 bar. Whenthe pressure no longer changes, the reactor is put under reducedpressure while still maintaining vigorous stirring of the moltenreactants. The reaction is monitored as previously in the case of thetwo-step process.

The proper ratio of polyamide to polyether blocks can be found in asingle poly(ether block amide), or a blend of two or more differentcomposition poly(ether block amide)s can be used with the proper averagecomposition. It can be useful to blend a block copolymer having a highlevel of polyamide groups with a block copolymer having a higher levelof polyether blocks, to produce a blend having an average level ofpolyether blocks of about 20 to 40 wt percent of the total blend ofpoly(amid-block-ether) copolymers, and preferably about 30 to 35 wtpercent. The copolymer can comprise a blend of two differentpoly(ether-block-amide)s comprising at least one block copolymer havinga level of polyether blocks below about 35 wt percent, and a secondpoly(ether-block-amide) having at least about 45 wt percent of polyetherblocks.

The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a melting temperature (T_(m)) from about 90degrees centigrade to about 120 degrees centigrade when determined inaccordance with ASTM D3418-97 as described herein below. Thethermoplastic elastomer can be a polyamide or a poly(ether-block-amide)with a melting temperature (T_(m)) from about 93 degrees C. to about 99degrees C. when determined in accordance with ASTM D3418-97 as describedherein below. The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a melting temperature (T_(m)) from about112 degrees C. to about 118 degrees C. when determined in accordancewith ASTM D3418-97 as described herein below. The thermoplasticelastomer can be a polyamide or a poly(ether-block-amide) with a meltingtemperature of about 90 degrees C., about 91 degrees C., about 92degrees C., about 93 degrees C., about 94 degrees C., about 95 degreesC., about 96 degrees C., about 97 degrees C., about 98 degrees C., about99 degrees C., about 100 degrees C., about 101 degrees C., about 102degrees C., about 103 degrees C., about 104 degrees C., about 105degrees C., about 106 degrees C., about 107 degrees C., about 108degrees C., about 109 degrees C., about 110 degrees C., about 111degrees C., about 112 degrees C., about 113 degrees C., about 114degrees C., about 115 degrees C., about 116 degrees C., about 117degrees C., about 118 degrees C., about 119 degrees C., about 120degrees C., any range of melting temperature (T_(m)) values encompassedby any of the foregoing values, or any combination of the foregoingmelting temperature (T_(m)) values, when determined in accordance withASTM D3418-97 as described herein below.

The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a glass transition temperature (T_(g)) fromabout −20 degrees C. to about 30 degrees C. when determined inaccordance with ASTM D3418-97 as described herein below. Thethermoplastic elastomer can be a polyamide or a poly(ether-block-amide)with a glass transition temperature (T_(g)) from about −13 degrees C. toabout −7 degrees C. when determined in accordance with ASTM D3418-97 asdescribed herein below. The thermoplastic elastomer can be a polyamideor a poly(ether-block-amide) with a glass transition temperature (T_(g))from about 17 degrees C. to about 23 degrees C. when determined inaccordance with ASTM D3418-97 as described herein below. Thethermoplastic elastomer can be a polyamide or a poly(ether-block-amide)with a glass transition temperature (T_(g)) of about −20 degrees C.,about −19 degrees C., about −18 degrees C., about −17 degrees C., about−16 degrees C., about −15 degrees C., about −14 degrees C., about −13degrees C., about −12 degrees C., about −10 degrees C., about −9 degreesC., about −8 degrees C., about −7 degrees C., about −6 degrees C., about−5 degrees C., about −4 degrees C., about −3 degrees C., about −2degrees C., about −1 degrees C., about 0 degrees C., about 1 degrees C.,about 2 degrees C., about 3 degrees C., about 4 degrees C., about 5degrees C., about 6 degrees C., about 7 degrees C., about 8 degrees C.,about 9 degrees C., about 10 degrees C., about 11 degrees C., about 12degrees C., about 13 degrees C., about 14 degrees C., about 15 degreesC., about 16 degrees C., about 17 degrees C., about 18 degrees C., about19 degrees C., about 20 degrees C., any range of glass transitiontemperature values encompassed by any of the foregoing values, or anycombination of the foregoing glass transition temperature values, whendetermined in accordance with ASTM D3418-97 as described herein below.

The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) that can be spun into a yarn when tested in amelt extruder.

The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a melt flow index from about 10 cm³/10 minto about 30 cm³/10 min when tested in accordance with ASTM D1238-13 asdescribed herein below at 160 degrees C. using a weight of 2.16 kg. Thethermoplastic elastomer can be a polyamide or a poly(ether-block-amide)with a melt flow index from about 22 cm³/10 min to about 28 cm³/10 minwhen tested in accordance with ASTM D1238-13 as described herein belowat 160 degrees C. using a weight of 2.16 kg. The thermoplastic elastomercan be a polyamide or a poly(ether-block-amide) with a melt flow indexof about 10 cm³/10 min, about 11 cm³/10 min, about 12 cm³/10 min, about13 cm³/10 min, about 14 cm³/10 min, about 15 cm³/10 min, about 16 cm³/10min, about 17 cm³/10 min, of about 18 cm³/10 min, about 19 cm³/10 min,of about 20 cm³/10 min, about 21 cm³/10 min, about 22 cm³/10 min, about23 cm³/10 min, about 24 cm³/10 min, about 25 cm³/10 min, about 26 cm³/10min, about 27 cm³/10 min, of about 28 cm³/10 min, about 29 cm³/10 min,of about 30 cm³/10 min, any range of melt flow index values encompassedby any of the foregoing values, or any combination of the foregoing meltflow index values, when determined in accordance with ASTM D1238-13 asdescribed herein below at 160 degrees C. using a weight of 2.16 kg.

The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a cold Ross flex test result of about120,000 to about 180,000 when tested on a thermoformed plaque of thepolyamide or the poly(ether-block-amide) in accordance with the coldRoss flex test as described herein below. The thermoplastic elastomercan be a polyamide or a poly(ether-block-amide) with a cold Ross flextest result of about 140,000 to about 160,000 when tested on athermoformed plaque of the polyamide or the poly(ether-block-amide) inaccordance with the cold Ross flex test as described herein below. Thethermoplastic elastomer can be a polyamide or a poly(ether-block-amide)with a cold Ross flex test result of about 130,000 to about 170,000 whentested on a thermoformed plaque of the polyamide or thepoly(ether-block-amide) in accordance with the cold Ross flex test asdescribed herein below. The thermoplastic elastomer can be a polyamideor a poly(ether-block-amide) with a cold Ross flex test result of about120,000, about 125,000, about 130,000, about 135,000, about 140,000,about 145,000, about 150,000, about 155,000, about 160,000, about165,000, about 170,000, about 175,000, about 180,000, any range of coldRoss flex test values encompassed by any of the foregoing values, or anycombination of the foregoing cold Ross flex test values, when tested ona thermoformed plaque of the polyamide or the poly(ether-block-amide) inaccordance with the cold Ross flex test as described herein below.

The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a modulus from about 5 MPa to about 100 MPawhen determined on a thermoformed plaque in accordance with ASTM D412-98Standard Test Methods for Vulcanized Rubber and Thermoplastic Rubbersand Thermoplastic Elastomers-Tension with modifications described hereinbelow. The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a modulus from about 20 MPa to about 80 MPawhen determined on a thermoformed plaque in accordance with ASTM D412-98Standard Test Methods for Vulcanized Rubber and Thermoplastic Rubbersand Thermoplastic Elastomers-Tension with modifications described hereinbelow. The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a modulus of about 5 MPa, about 10 MPa,about 15 MPa, about 20 MPa, about 25 MPa, about 30 MPa, about 35 MPa,about 40 MPa, about 45 MPa, about 50 MPa, about 55 MPa, about 60 MPa,about 65 MPa, about 70 MPa, about 75 MPa, about 80 MPa, about 85 MPa,about 90 MPa, about 95 MPa, about 100 MPa, any range of modulus valuesencompassed by any of the foregoing values, or any combination of theforegoing modulus values, when tested on a thermoformed plaque of thepolyamide or the poly(ether-block-amide) in accordance with ASTM D412-98Standard Test Methods for Vulcanized Rubber and Thermoplastic Rubbersand Thermoplastic Elastomers-Tension with modifications described hereinbelow.

The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a melting temperature (T_(m)) of about 115degrees C. when determined in accordance with ASTM D3418-97 as describedherein below; a glass transition temperature (T_(g)) of about −10degrees C. when determined in accordance with ASTM D3418-97 as describedherein below; a melt flow index of about 25 cm³/10 min when tested inaccordance with ASTM D1238-13 as described herein below at 160 degreesC. using a weight of 2.16 kg; a cold Ross flex test result of about150,000 when tested on a thermoformed plaque in accordance with the coldRoss flex test as described herein below; and a modulus from about 25MPa to about 70 MPa when determined on a thermoformed plaque inaccordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubberand Thermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below.

The thermoplastic elastomer can be a polyamide or apoly(ether-block-amide) with a melting temperature (T_(m)) of about 96degrees C. when determined in accordance with ASTM D3418-97 as describedherein below; a glass transition temperature (T_(g)) of about 20 degreesC. when determined in accordance with ASTM D3418-97 as described hereinbelow; a cold Ross flex test result of about 150,000 when tested on athermoformed plaque in accordance with the cold Ross flex test asdescribed herein below; and a modulus of less than or equal to about 10M Pa a when determined on a thermoformed plaque in accordance with ASTMD412-98 Standard Test Methods for Vulcanized Rubber and ThermoplasticRubbers and Thermoplastic Elastomers-Tension with modificationsdescribed herein below.

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of VESTAMID® (EvonikIndustries); PELATAMID® (Arkema), e.g., product code H2694; PEBAX®(Arkema), e.g., product code “PEBAX MH1657” and “PEBAX MV1074”; PEBAX®RNEW (Arkema); GRILAMID® (EMS-Chemie AG), or also to other similarmaterials produced by various other suppliers.

Thermoplastic Polyolefin Elastomers

In some aspects, the thermoplastic elastomers can comprise or consistessentially of a thermoplastic polyolefin. Exemplary of thermoplasticpolyolefins useful in the disclosed second polymeric materials caninclude, but are not limited to, thermoplastic olefin elastomers (e.g.,metallocene-catalyzed block copolymers of ethylene and α-olefins having4 to about 8 carbon atoms). The thermoplastic polyolefin can be apolymer comprising an ethylene-α-olefin copolymer, an ethylene-propylenerubber (EPDM), a polybutene, a polyisobutylene, apoly-4-methylpent-1-ene, a polyisoprene, a polybutadiene, aethylene-methacrylic acid copolymer, and an olefin elastomer such as adynamically cross-linked polymer obtained from polypropylene (PP) and anethylene-propylene rubber (EPDM), and blends or mixtures of theforegoing. Further exemplary thermoplastic polyolefins useful in thedisclosed second polymeric materials are polymers of cycloolefins suchas cyclopentene or norbornene.

The polyolefin can be a polyethylene copolymer derived from monomers ofmonolefins and diolefins copolymerized with a vinyl, acrylic acid,methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinyl acetate.Polyolefin copolymers comprising vinyl acetate-derived units can be ahigh vinyl acetate content copolymer, e.g., greater than about 50 wtpercent vinyl acetate-derived composition.

The thermoplastic polyolefin, as disclosed herein, can be formed throughfree radical, cationic, and/or anionic polymerization by methods wellknown to those skilled in the art (e.g., using a peroxide initiator,heat, and/or light). The disclosed thermoplastic polyolefin can beprepared by radical polymerization under high pressure and at elevatedtemperature. Alternatively, the thermoplastic polyolefin can be preparedby catalytic polymerization using a catalyst that normally contains oneor more metals from group IVb, Vb, VIb or VIII metals. The catalystusually has one or more than one ligand, typically oxides, halides,alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls thatcan be either p- or s-coordinated complexed with the group IVb, Vb, VIbor VIII metal. The metal complexes can be in the free form or fixed onsubstrates, typically on activated magnesium chloride, titanium(III)chloride, alumina or silicon oxide. It is understood that the metalcatalysts can be soluble or insoluble in the polymerization medium. Thecatalysts can be used by themselves in the polymerization or furtheractivators can be used, typically a group Ia, IIa and/or IIIa metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes. The activators can be modified conveniently with furtherester, ether, amine or silyl ether groups.

Suitable thermoplastic polyolefins can be prepared by polymerization ofmonomers of monolefins and diolefins as described herein. Exemplarymonomers that can be used to prepare disclosed thermoplastic polyolefininclude, but are not limited to, ethylene, propylene, 1-butene,1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene,4-methyl-1-pentene, 5-methyl-1-hexene and mixtures thereof.

Suitable ethylene-α-olefin copolymers can be obtained bycopolymerization of ethylene with an α-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

The thermoplastic polyolefin can be a mixture of thermoplasticpolyolefins, such as a mixture of two or more polyolefins disclosedherein above. For example, a suitable mixture of thermoplasticpolyolefins can be a mixture of polypropylene with polyisobutylene,polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) ormixtures of different types of polyethylene (for example LDPE/HDPE).

The thermoplastic polyolefin can be a copolymer of suitable monolefinmonomers or a copolymer of a suitable monolefin monomer and a vinylmonomer. Exemplary thermoplastic polyolefin copolymers include, but arenot limited to, ethylene/propylene copolymers, linear low densitypolyethylene (LLDPE) and mixtures thereof with low density polyethylene(LDPE), propylene/but-1-ene copolymers, propylene/isobutylenecopolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers,ethylene/methylpentene copolymers, ethylene/heptene copolymers,ethylene/octene copolymers, propylene/butadiene copolymers,isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers,ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetatecopolymers and their copolymers with carbon monoxide or ethylene/acrylicacid copolymers and their salts (ionomers) as well as terpolymers ofethylene with propylene and a diene such as hexadiene, dicyclopentadieneor ethylidene-norbornene; and mixtures of such copolymers with oneanother and with polymers mentioned in 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA),LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbonmonoxide copolymers and mixtures thereof with other polymers, forexample polyamides.

The second polymeric material can include one or more olefinic polymers.Olefinic polymers can include ethylene-based copolymers, propylene-basedcopolymers, and butene-based copolymers. The olefinic polymer can be anethylene-based copolymer such as a styrene-ethylene/butylene-styrene(SEBS) copolymer; an ethylene-propylene diene monomer (EPDM) copolymer;an ethylene-vinyl acetate (EVA) copolymer; an ethylene alkyl acrylate(EAA) copolymer; an ethylene alkyl methacrylate (EAMA) copolymer; anycopolymer thereof, and any blend thereof.

The second polymeric material can include an ethylene-vinyl acetate(EVA) copolymer. The ethylene-vinyl acetate (EVA) copolymer can have arange of vinyl acetate contents, for example about 50 percent to about90 percent, about 50 percent to about 80 percent, about 5 percent toabout 50 percent, about 10 percent to about 45 percent, about 10 percentto about 30 percent, about 30 percent to about 45 percent, or about 20percent to about 35 percent.

The polyolefin can be a polypropylene. The term “polypropylene,” as usedherein, is intended to encompass any polymeric composition comprisingpropylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as ethylene, butylene, and the like). Such a term also encompassesany different configuration and arrangement of the constituent monomers(such as atactic, syndiotactic, isotactic, and the like). Thus, the termas applied to fibers is intended to encompass actual long strands,tapes, threads, and the like, of drawn polymer. The polypropylene can beof any standard melt flow (by testing); however, standard fiber gradepolypropylene resins possess ranges of Melt Flow Indices between about 1and 1000.

The polyolefin can be a polyethylene. The term “polyethylene,” as usedherein, is intended to encompass any polymeric composition comprisingethylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as propylene, butylene, and the like). Such a term alsoencompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

Thermoplastic Ionomer Elastomers

In certain aspects, the thermoplastic elastomer can be one or moreionomeric polymers. The ionomeric polymers can include chain unitsderived from one or more olefins and chain units derived from one ormore ethylenically-unsaturated acid groups. The compositions can alsoinclude a plurality of cations ionically crosslink anionic form of theacid groups in the ionomeric copolymers. The compositions can beessentially just the ionomeric copolymers and metal cations. Theionomeric copolymers can have a melt flow index of about 30 or less,about 20 or less, about 15 or less, about 10 or less, or about 5 orless.

The ionomeric copolymers can be terpolymers of ethylene, acrylic acid,and methyl acrylate or butyl acrylate. In some aspects, a ratio III of atotal parts by weight of the acrylic acid in the ionomeric copolymers toa total weight of the ionomeric copolymers is about 0.05 to about 0.6,about 0.1 to about 0.6, about 0.1 to about 0.5, about 0.15 to about 0.5,or about 0.2 to about 0.5.

The ionomeric copolymers can have a plurality of a first repeat unithaving a formula according to Formula 23 and a plurality of a secondrepeat unit having a formula according to Formula 24, and a plurality ofcations, wherein each of the cations is crosslinking two or more of thesecond repeat units.

Each occurrence of R¹ can be independently none, a substituted orunsubstituted C₁, C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkyl, or a substitutedor unsubstituted C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkenyl. In some aspects,each occurrence of R¹ is none.

Each occurrence of R² can be independently hydrogen, a halogen, asubstituted or unsubstituted C₁, C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkyl, asubstituted or unsubstituted C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkenyl, asubstituted or unsubstituted phenyl, a substituted or unsubstitutedalkyl-phenyl, a substituted or unsubstituted C₁, C₂, C₃, C₄, C₅, C₆, C₇,or C₈ alkoxy, or a substituted or unsubstituted C₃, C₄, C₅, C₆, C₇, orC₈, C₉, C₁₀, C₁₁, or C₁₂ alkyl ester. In some aspects, each occurrenceof R² is independently a hydrogen, methyl, phenyl, or halogen. In someaspects, each occurrence of R² has a structure given by the formula:

where each occurrence of R⁴ is independently a hydrogen, a substitutedor unsubstituted C₁, C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkyl.

Each occurrence of R³ can be independently hydrogen, a substituted orunsubstituted C₁, C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkyl, or a substitutedor unsubstituted C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkenyl. In some aspects,each occurrence of R³ is independently a hydrogen or methyl.

Each occurrence of R⁵ can be independently a hydrogen, a halogen, asubstituted or unsubstituted C₁, C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkyl, asubstituted or unsubstituted C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkenyl, asubstituted or unsubstituted phenyl, a substituted or unsubstitutedalkyl-phenyl, a substituted or unsubstituted C₁, C₂, C₃, C₄, C₅, C₆, C₇,or C₈ alkoxy, or a substituted or unsubstituted C₃, C₄, C₅, C₆, C₇, orC₈, C₉, C₁₀, C₁₁, or C₁₂ alkyl ester. In some aspects, each occurrenceof R⁵ is independently a hydrogen or a methyl.

Each occurrence of R⁶ can be independently none, a substituted orunsubstituted C₁, C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkyl, a substituted orunsubstituted C₂, C₃, C₄, C₅, C₆, C₇, or C₈ alkenyl, a substituted orunsubstituted phenyl, a substituted or unsubstituted alkyl-phenyl, or asubstituted or unsubstituted C₁-C₈ alkoxy. In some aspects, eachoccurrence of R⁶ is none.

Each occurrence of R⁷ can be independently a carboxylate, a sulfate, asulfonate, a nitrate, a phosphate, a phosphonate, or another negativelycharged functional group. In some aspects, each occurrence of R⁷ is acarboxylate. For example, the second repeat unit can have a formulaaccording to Formula 25, where R⁵ and R⁶ are as descried above.

The compositions can include a plurality of cations ionicallycrosslinking the ionomeric copolymers. For example, the cations canionically crosslink anionic groups from acid groups. The cationsionically crosslink units having a structure according to Formula II.

In the compositions described herein, a plurality of cations are presentto crosslink negatively charged groups in the ionomeric copolymer. Forexample, an ionomer having free carboxylate groups can be crosslinked bya plurality of cations. Because the compositions are crosslinked viaionic crosslinking, the compositions are in some aspects free orsubstantially free of any covalent and irreversible chemical crosslinks,for example the compositions can be free of covalent crosslinkingbetween the ionomeric copolymers. The cations can include cations ofalkali metals or alkali earth metals such as a magnesium ion, a sodiumion, a potassium ion, a cesium ion, a calcium ion, a barium ion, amanganese ion, a copper ion, a zinc ion, a tin ion, a lithium ion, and apositively charged compound thereof. The cation can be a sodium cation,a lithium cation, a zinc cation, a magnesium cation, or any combinationthereof. The cations can include organic cations such as an ammoniumion, a pyridinium ion, a guanidinium ion, an imidazolium ion, aphosphonium ion, or a sulfonium ion.

In some aspects, a ratio II of a total parts by weight of the carboxylicacid groups in the ionomeric copolymers to a total weight of theionomeric copolymers is about 0.05 to about 0.7, about 0.1 to about 0.6,about 0.2 to about 0.6, or about 0.2 to about 0.5. In some aspects, aratio II of a total parts by weight of the second repeat units in theionomeric copolymers to a total weight of the ionomeric copolymers isabout 0.1 to about 0.7, about 0.1 to about 0.6, about 0.2 to about 0.6,or about 0.2 to about 0.5.

The second polymeric material can include one or more ionomers, such asany of the “SURLYN” polymers (DuPont, Wilmington, Del., USA.

The second polymeric material can include acrylic block copolymerelastomers, such as block copolymers comprising a first PMMA block, anacrylate block, and a second PMMA block.

Thermoplastic Styrenic Copolymer Elastomers

In certain aspects, the thermoplastic elastomer is a thermoplasticelastomeric styrenic copolymer. Examples of these copolymers include,but are not limited to, styrene butadiene styrene (SBS) block copolymer,a styrene ethylene/butylene styrene (SEBS) resin, a polyacetal resin(POM) or a styrene acrylonitrile resin (SAN). Exemplary commerciallyavailable thermoplastic elastomeric styrenic copolymers includeMONOPRENE IN5074, SP066070, and SP16975 (Teknor Apex), which are styreneethylene/butylene styrene (SEBS) resins.

Thermoplastic Vulcanizate Materials

The second polymeric material can include an injection processiblethermoplastic vulcanizate (TPV) material. Injection-processible TPVmaterials are typically cross-linked or partially cross-linked rubbersdispersed into thermoplastic host phases. Exemplary TPV materialsinclude ethylene propylene diene rubber in polypropylene hosts(EPDM/PP), such as “SARLINK” or “SANTOPRENE” TPV materials. Otherexemplary TPV materials include alkyl acrylic copolymer rubbers inpolyamide hosts (ACM/PA), such as “ZEOTHERM” TPVs. Yet other exemplaryTPV materials include silicone rubbers dispersed in “HYTREL” basedcopolyesters (e.g., so-called TSiPVs).

Additives.

In various aspects, the disclosed thermoplastic copolyester compositionsand second polymeric material can independently further comprise anadditive. The additive can be incorporated directly into the disclosedthermoplastic copolyester composition or polymeric layer, oralternatively, applied thereto, prior to foaming the thermoplasticcopolyester composition or second polymeric material. Additives that canbe used in the disclosed compositions and materials include, but are notlimited to, dyes, pigments, colorants, ultraviolet light absorbers,hindered amine light stabilizers, antioxidants, processing aids oragents, plasticizers, lubricants, emulsifiers, pigments, dyes, opticalbrighteners, rheology additives, catalysts, flow-control agents, slipagents, crosslinking agents, crosslinking boosters, halogen scavengers,smoke inhibitors, flameproofing agents, antistatic agents, fillers, ormixtures of two or more of the foregoing. In some aspects, the additivecan be a wax, an anti-oxidant, a UV-absorbing agent, a coloring agent,or combinations thereof.

The additive can be present in an amount from about 0.1 weight percentto about 10 weight percent, or from 0.1 to 6 weight percent, based onthe total weight of the composition or material; or any weight percentvalue or set of weight percent values within any of the foregoing rangesof weight percent, or any range of weight percent values encompassing asub-set of any of the foregoing ranges. In a particular aspect, theadditive can be present in the composition or material in an amount fromabout 0.1 weight percent to about 4 weight percent, based on a totalweight of the composition or material. The composition or material cancomprise less than 4 weight percent, or less than 3 weight percent, orless than 2 weight percent of additives, based on a total weight of thecomposition or material. The composition or material can be essentiallyfree of additives.

In some instances, an additive can be present in an amount of from about0.01 weight percent to about 10 weight percent, about 0.025 weightpercent to about 5 weight percent, or about 0.1 weight percent to 3weight percent, where the weight percent is based upon the sum of thematerial components in the thermoplastic copolyester composition, orsecond polymeric material.

Individual components can be mixed together with the other components ofthe thermoplastic copolyester composition or second polymeric materialin a continuous mixer or a batch mixer, e.g., in an intermeshing rotormixer, such as an Intermix mixer, a twin screw extruder, in a tangentialrotor mixer such as a Banbury mixer, using a two-roll mill, or somecombinations of these to make a composition comprising a thermoplasticpolymer and an additive. The mixer can blend the components together viaa single step or multiple steps, and can mix the components viadispersive mixing or distributive mixing to form the resultingthermoplastic composition. This step is often referred to as“compounding.”

The thermoplastic copolyester composition and second polymeric materialcan independently further comprise a solid non-polymeric material suchas a chemical blowing agent, nucleating agent, filler, or a combinationthereof. The solid non-polymeric material can be present in an amountfrom about 0.05 weight percent to about 20 weight percent based on thetotal weight of the composition or material; about 0.1 weight percent toabout 10 weight percent based on the total weight of the composition ormaterial. The foamed polymeric material can comprise less than about 5weight percent, or less than 4 weight percent, or less than 3 weightpercent, or less than 2 weight percent, or less than 1 weight percent ofsolid non-polymeric material, based on the total weight of thethermoplastic copolyester composition or second polymeric material; orany weight percent value or set of weight percent values within any ofthe foregoing ranges of weight percent, or any range of weight percentvalues encompassing a sub-set of any of the foregoing ranges.

The thermoplastic copolyester composition or second polymeric materialcan comprise essentially no non-polymeric material such as a chemicalblowing agent, nucleating agent, filler, or a combination thereof. Inother words, the composition or material can be essentially free ofnon-polymeric materials. In other instances, the composition or materialcan comprise less than about 10 weight percent of a non-polymericmaterial such as a chemical blowing agent, nucleating agent, filler, ora combination thereof. The composition or material can comprise lessthan 4 weight percent, or less than 3 weight percent, or less than 2weight percent of non-polymeric material, based on a total weight of thecomposition or material.

In some instances, the solid non-polymeric material is a filler. Thefiller can be a particulate filler. In further aspects, the filler is acarbonaceous filler. The carbonaceous filler can be carbon black,activated carbon, graphite, carbon fibers, carbon fibrils, carbonnanoparticles, or combinations thereof. In various aspects, thecarbonaceous filler can be chemically-modified. Alternatively, thefiller can be an inorganic filler. The inorganic filler can be an oxide,a hydroxide, a salt, a silicate, a metal, or combinations thereof.Examples of an inorganic filler include, but are not limited to, glassspheres, glass fibers, glass hollow spheres, glass flakes, MgO, SiO₂,Sb₂O₃, Al₂O₃, ZnO, talc, mica, kaolin, wollastonite, or combinationsthereof.

Nucleating agents are widely used to modify the properties of variouspolymers. Nucleating agents can aid in decreasing foam specific gravity,increasing the number of cells present in the foam, and decreasing cellsize in the foam by providing a surface for heterogeneous nucleation ofgas bubbles from the supercritical fluid state. For the thermoplasticcopolyester compositions and second polymeric materials of the presentdisclosure, nucleating agents can influence the properties of the finalfoam article by modifying the quantity, distribution and rate ofsupercritical fluid conversion from a liquid to a gas during the foamingprocess as lower pressures. The addition of nucleating agents provides asurface on which the supercritical fluid can be transformed from aliquid to a gas. As a consequence, many nucleation sites will result inmany gas cell domains. In a particular example, the nucleating agent caninclude a metal salt of a fatty acid. In some aspects, the nucleatingagent is zinc stearate. In some aspects, the composition or materialcontains about 0.1 weight percent to about 10 weight percent, about 0.1weight percent to about 5 weight percent, about 0.1 weight percent toabout 2 weight percent, or about 0.5 weight percent to about 2 weightpercent of the nucleating agent based upon a total weight of thecomposition or material.

In some aspects, the additive is a nucleating agent such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals, ormixtures thereof. Alternatively, the nucleating agent can be a mono- orpolycarboxylic acids, and the salts thereof, e.g., 4-tert-butylbenzoicacid, adipic acid, diphenylacetic acid, sodium succinate, sodiumbenzoate, or mixtures thereof. In a further aspect, the additive can bea nucleating agent comprising both an inorganic and an organic materialas disclosed herein above.

In some aspects, the rheology modifier can be a nano-particles havingcomparatively high aspect ratios, nano-clays, nano-carbon, graphite,nano-silica, and the like.

In some aspects, the additive is a filler or reinforcing agent such asclay, kaolin, talc, asbestos, graphite, glass (such as glass fibers,glass particulates, and glass bulbs, spheres, or spheroids), mica,calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide,silicates, diatomaceous earth, carbonates (such as calcium carbonate,magnesium carbonate and the like), metals (such as titanium, tungsten,zinc, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron,bronze, cobalt, beryllium, and alloys of these), metal oxides (such aszinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide,zirconium oxide and the like), metal hydroxides, particulate syntheticplastics (such as polyethylene, polypropylene, polystyrene, polyamide,polyester, polyurethane, polyimide, and the like), synthetic fibers(such as fibers comprising high molecular weight polyethylene,polypropylene, polystyrene, polyamide, polyester, polyurethane,polyimide, and the like), particulate carbonaceous materials (such ascarbon black and the like), wood flour and flours or fibers of othernatural products, as well as cotton flock, non-cotton cellulose flock,cellulose pulp, leather fiber, and combinations of any of the above.Non-limiting examples of heavy density filler components that can beused to increase the specific gravity of the cured elastomer compositioncan include titanium, tungsten, aluminum, bismuth, nickel, molybdenum,iron, steel, lead, copper, brass, boron, boron carbide whiskers, bronze,cobalt, beryllium, zinc, tin, metal oxides (such as zinc oxide, ironoxide, aluminum oxide, titanium oxide, magnesium oxide, and zirconiumoxide), metal sulfates (such as barium sulfate), metal carbonates (suchas calcium carbonate), and combinations of these. Non-limiting examplesof light density filler components that can be used to decrease thespecific gravity of the elastomer compound can include particulateplastics, hollow glass spheres, ceramics, and hollow spheres, regrinds,and foams, which can be used in combinations.

In some examples, the disclosed foamed polymeric materials can alsoinclude a nanofiller. Nanofillers can not only serve as mechanicalreinforcement but also nucleating agents. A variety of nanofillers canbe used in lieu of or in addition to the zinc stearate. Nanofillers caninclude nanomaterials having one-dimensional structures such as ofplates, laminas and/or shells; two-dimensional structures such asnanotubes and nanofibres having a diameter lower than 0.1 micrometer; orthree-dimensional nanostructures such as nanoparticles or beads.Nanoplate fillers can be natural or synthetic clays, as well asphosphates of transition metals. Clay-based nanocomposites generate anoverall improvement in physical performances. The most widely used onesare the phyllosilicates. Nanofillers can include nano-oxides such asnanoparticles of Titanium dioxide or Rutile. Other nanofillers caninclude nanoparticles of alumina or aluminum oxide, diatomite, andnanoscale carbon materials such as single-wall carbon nanotubes (SWCNT)or double-wall carbon nanotubes (DWCNT).

Definitions

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. It will be further understoodthat terms, such as those defined in commonly used dictionaries, shouldbe interpreted as having a meaning that is consistent with their meaningin the context of the specification and relevant art and should not beinterpreted in an idealized or overly formal sense unless expresslydefined herein.

The terms “comprises,” “comprising,” “including,” and “having,” areinclusive and therefore specify the presence of features, steps,operations, elements, and/or components, but do not preclude thepresence or addition of one or more other features, steps, operations,elements, components, and/or groups thereof.

As used in the specification and the appended claims, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a foam particle,”“a midsole,” or “an adhesive,” including, but not limited to, two ormore such foam particles, midsoles, or adhesives, and the like.

As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items.

As used herein, in substance or substantially means at least 50 percent,60 percent, 75 percent, 90 percent, 95 percent, or more, as determinedbased on weight or volume.

The terms first, second, third, etc. can be used herein to describevarious elements, components, regions, layers and/or sections. Theseelements, components, regions, layers and/or sections should not belimited by these terms. These terms can be only used to distinguish oneelement, component, region, layer or section from another region, layeror section. Terms such as “first,” “second,” and other numerical termsdo not imply a sequence or order unless clearly indicated by thecontext. Thus, a first element, component, region, layer or sectiondiscussed below could be termed a second element, component, region,layer or section without departing from the teachings of the exampleconfigurations.

As used herein, the modifiers “upper,” “lower,” “top,” “bottom,”“upward,” “downward,” “vertical,” “horizontal,” “longitudinal,”“transverse,” “front,” “back” etc., unless otherwise defined or madeclear from the disclosure, are relative terms meant to place the variousstructures or orientations of the structures of the article of footwearin the context of an article of footwear worn by a user standing on aflat, horizontal surface.

The term “receiving”, such as for “receiving an upper for an article offootwear”, when recited in the claims, is not intended to require anyparticular delivery or receipt of the received item. Rather, the term“receiving” is merely used to recite items that will be referred to insubsequent elements of the claim(s), for purposes of clarity and ease ofreadability.

The terms “at least one” and “one or more of” an element are usedinterchangeably, and have the same meaning that includes a singleelement and a plurality of the elements, and can also be represented bythe suffix “(s)” at the end of the element. For example, “at least onepolyamide”, “one or more polyamides”, and “polyamide(s)” can be usedinterchangeably and have the same meaning.

It should be noted that ratios, concentrations, amounts, and othernumerical data can be expressed herein in a range format. Where thestated range includes one or both of the limits, ranges excluding eitheror both of those included limits are also included in the disclosure,e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well asthe range greater than ‘x’ and less than ‘y’. The range can also beexpressed as an upper limit, e.g. ‘about x, y, z, or less’ and should beinterpreted to include the specific ranges of ‘about x’, ‘about y’, and‘about z’ as well as the ranges of ‘less than x’, less than y′, and‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ shouldbe interpreted to include the specific ranges of ‘about x’, ‘about y’,and ‘about z’ as well as the ranges of ‘greater than x’, greater thany′, and ‘greater than z’. In addition, the phrase “about ‘x’ to ‘y’”,where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about‘y’”. It is to be understood that such a range format is used forconvenience and brevity, and thus, should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. To illustrate, anumerical range of “about 0.1% to 5%” should be interpreted to includenot only the explicitly recited values of about 0.1 percent to about 5percent, but also include individual values (e.g., 1 percent, 2 percent,3 percent, and 4 percent) and the sub-ranges (e.g., 0.5 percent, 1.1percent, 2.4 percent, 3.2 percent, and 4.4 percent) within the indicatedrange.

The terms “about” and “substantially” are used herein with respect tomeasurable values and ranges due to expected variations known to thoseskilled in the art (e.g., limitations and variabilities inmeasurements).

As used herein, the terms “optional” or “optionally” means that thesubsequently described component, event or circumstance can or cannotoccur, and that the description includes instances where said component,event or circumstance occurs and instances where it does not.

As used herein, the term “units” can be used to refer to individual(co)monomer units such that, for example, styrenic repeat units refersto individual styrene (co)monomer units in the polymer. In addition, theterm “units” can be used to refer to polymeric block units such that,for example, “styrene repeating units” can also refer to polystyreneblocks; “units of polyethylene” refers to block units of polyethylene;“units of polypropylene” refers to block units of polypropylene; “unitsof polybutylene” refers to block units of polybutylene, and so on. Suchuse will be clear from the context.

The term “copolymer” refers to a polymer having two or more monomerspecies, and includes terpolymers (i.e., copolymers having three monomerspecies).

Reference to “a” chemical compound refers one or more molecules of thechemical compound, rather than being limited to a single molecule of thechemical compound. Furthermore, the one or more molecules may or may notbe identical, so long as they fall under the category of the chemicalcompound. Thus, for example, “a” polyamide is interpreted to include oneor more polymer molecules of the polyamide, where the polymer moleculesmay or may not be identical (e.g., different molecular weights and/orisomers).

As used herein the terms “percent by weight” or “weight percent,” whichcan be used interchangeably, indicate the weight percent of a givencomponent based on the total weight of the composition or article,unless otherwise specified. That is, unless otherwise specified, allweight percent values are based on the total weight of the composition.It should be understood that the sum of weight percent values for allcomponents in a disclosed composition or formulation or article areequal to 100.

Similarly, the terms “percent by volume” or “volume percent,” which canbe used interchangeably, indicate the percent by volume of a givencomponent based on the total volume of the composition or article,unless otherwise specified. That is, unless otherwise specified, allvolume percent values are based on the total volume of the compositionor article. It should be understood that the sum of volume percentvalues for all components in a disclosed composition or formulation orarticle are equal to 100.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valence filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group. Unless defined otherwise,technical and scientific terms used herein have the same meaning as iscommonly understood by one of skill in the art to which this inventionbelongs.

Unless otherwise specified, temperatures referred to herein are based onatmospheric pressure (i.e. one atmosphere).

Before proceeding to the Examples, it is to be understood that thisdisclosure is not limited to particular aspects described, and as suchmay, of course, vary. Other systems, methods, features, and advantagesof foam compositions and components thereof will be or become apparentto one with skill in the art upon examination of the following drawingsand detailed description. It is intended that all such additionalsystems, methods, features, and advantages be included within thisdescription, be within the scope of the present disclosure, and beprotected by the accompanying claims. It is also to be understood thatthe terminology used herein is for the purpose of describing particularaspects only, and is not intended to be limiting. The skilled artisanwill recognize many variants and adaptations of the aspects describedherein. These variants and adaptations are intended to be included inthe teachings of this disclosure and to be encompassed by the claimsherein.

Test Methods

Below are certain sampling procedures and testing methods referenced inthe Description and in the Examples.

Sampling Procedures

Various properties of the compositions and foams and other articlesformed therefrom can be characterized using samples prepared with thefollowing sampling procedures:

a. Neat Sampling Procedure

The neat sampling procedure can be used to obtain a neat sample of afoamed or unfoamed thermoplastic copolyester composition, an unfoamed orfoamed second polymeric material, or, in some instances, a sample of amaterial (e.g., polymer) used to form a thermoplastic copolyestercomposition or second polymeric material. The material can be providedin media form, such as flakes, granules, powders, pellets, and the like.If a source of the thermoplastic copolyester composition or secondpolymeric material is not available in a neat form, the sample can becut from another component containing the composition or material,thereby isolating a sample of the composition or material.

b. Plaque Sampling Procedure—Solid Composition or Material

The thermoplastic copolyester composition or second polymeric materialis molded into a plaque having dimensions of about six inches by about 4inches and a thickness of about 20 millimeters (or as otherwisespecified by the test method). The sample is prepared by mixing togetherthe components of the composition or material, melting the compositionor material, pouring, extruding, or injecting the melted compositioninto a mold cavity, cooling the melted composition or material tosolidify it in the mold cavity to form the plaque, and then removing theplaque from the mold cavity.

c. Plaque Sampling Procedure—Foam Composition or Material

The foamed thermoplastic copolyester composition or second polymericmaterial is foamed into a sheet. The skin is removed from a portion ofthe sheet, and the skinned portion of the sheet is cut into a plaquehaving dimensions of about six inches by about four inches and athickness of about 20 millimeter (mm) (or as otherwise specified by thetest method).

d. Component Sampling Procedure

This procedure can be used to obtain a sample of a foamed or unfoamedcomposition or material when the composition or material is incorporatedinto a component such as a sole structure or midsole or outsole of anarticle of footwear. A sample of the component which includes thecomposition or material is obtained as formed into the component, or cutfrom the article of footwear using a blade. This process is performed byseparating the component from an associated footwear upper, if present,and removing any materials from the article's top surface (e.g.,corresponding to the top surface). For example, the article's topsurface can be skinned, abraded, scraped, or otherwise cleaned to removeany upper adhesives, yarns, fibers, foams, and the like that couldpotentially interfere with the test results.

The resulting component sample includes the composition or material. Assuch, any test using a Component Sampling Procedure can simulate how thecomposition or material will perform as part of an article of footwear.As specified by the test method, the component may be tested as a fullcomponent (e.g., full midsole component), or it can be extracted as asample having a certain geometry. A sample of a component is taken at alocation along the component that provides a substantially constantthickness for the component (within plus or minus 10 percent of theaverage thickness), such as in a forefoot region, mid-foot region, or aheel region of the article. Unless otherwise specified, the desiredharvested geometry is a cylindrical puck with a 45-millimeter diameterand a cylinder height of at least about 10 millimeters, preferably fromabout 20 to 25 millimeters. Compression testing of the harvestedcomponent samples should be tested along the length of the cylinderusing compression platens that are at least twice the diameter of thecylindrical puck sample.

Solid Polymer, Thermoplastic Copolyester Composition, and SecondPolymeric Material Characterization.

Glass Transition Temperature, Melting Temperature Test

Dynamic scanning calorimetry (DSC) is performed on samples preparedusing the Neat Sampling Procedure, or on a portion of a sample preparedusing the Plaque Sampling Procedure or the Component Sampling Procedure.The test is conducted using a DSC system such as a TA instruments Q2000.10-30 mg samples are cycled from negative 90 degrees C. to 225 degreesC. at a rate of 20 degrees C./min and cooled to negative 90 degrees C.at a rate of 10 degrees C./min. Each sample is run in duplicate. Themelting temperature and glass transition temperature values are recordedfrom the second cycle. The melt “peak” was identified as the localmaximum of the second heating cycle. If there was more than one peak inthe DSC curve, the peak occurring at hotter temperatures was chosen asthe molding temperature reference. The tail was identified as theintersection of the tangent of the line of the higher temperature sideof the melt peak with the extrapolated baseline. A schematicillustrating the method for determining peak and tail temperatures isshown in FIG. 8.

Cyclic Tensile Test

The cyclic tensile testing is carried out on solid samples preparedusing the Plaque Sampling Procedure or the Component Sampling Procedure,having a dog-bone shape as described in ASTM D638 with a 2 mm thickness.In the test, the specimen is placed under a pre-load of 5 N. Strain iscontrolled to extend the sample to an extension 6 percent at a strainrate of 5 Hz. The stiffness is the load at 6 percent strain divided bythe extension at 6 percent strain, giving a value in N/mm. The maximumload (N) observed over the test cycle of 500 cycles is also recorded.

Melt Flow Index Test

The melt flow index is determined using a sample prepared using the NeatSampling Procedure, or on a portion of a sample prepared using thePlaque Sampling Procedure or the Component Sampling Procedure, accordingto the test method detailed in ASTM D1238-13 Standard Test Method forMelt Flow Rates of Thermoplastics by Extrusion Plastometer, usingProcedure A described therein. Briefly, the melt flow index measures therate of extrusion of thermoplastics through an orifice at a prescribedtemperature and load. In the test method, approximately 7 grams of thesample is loaded into the barrel of the melt flow apparatus, which hasbeen heated to a specified temperature of 210 degrees C., 220 degreesC., or 230 degrees C. A weight of 2.16 kilograms is applied to a plungerand the molten sample is forced through the die. A timed extrudate iscollected and weighed. Melt flow rate values are calculated in g/10 min,and are reported with the specified temperature (i.e., 210, 220 or 230degrees C.) and the weight applied to the plunger (i.e., 2.15kilograms).

Solid Polymer Abrasion Test (Akron)

Abrasion loss is tested on a sample sheet having a thickness of 3millimeters, prepared using the Plaque Sampling procedure or theComponent Sampling Procedure. The sample sheet is adhered onto an Akronabrasion test specimen with JIS-A hardness of 70 by using an adhesive toprepare a test specimen. Abrasion loss in volume is measured by using anAkron abrasion test machine at a load of 27N, an inclination angle of 15degree, a preliminary abrasion of 500 times and a test abrasion of 1,000times according to JIS K6254. The mass and/or volume of the sample ismeasured before and after the test, with the difference being theabrasion loss. The smaller the abrasion loss volume or mass, the betterthe abrasion resistance.

Solid Polymer Abrasion Test (DIN)

Abrasion loss is tested on cylindrical test pieces with a diameter of 16millimeters plus or minus 0.2 millimeters and a minimum thickness of 6mm cut from sheets using a ASTM standard hole drill. The abrasion lossis measured using Method B of ASTM D 5963-97a on a Gotech GT-7012-Dabrasion test machine. The tests are performed at 22 degrees C. with anabrasion path of 40 meters. The Standard Rubber #1 used in the tests hasa density of 1.336 grams per cubic centimeter (g/cm³). The smaller theabrasion loss volume, the better the abrasion resistance.

Solid Polymer Abrasion Test (DIN)

Abrasion loss is tested on samples cut from sheets having a minimumthickness of 6 millimeters to 12 millimeters, prepared using the PlaqueSampling Procedure or the Component Sampling Procedure. The cut sampleshave a cylindrical shape with a diameter of 16 millimeters plus or minus0.2 millimeters and a minimum thickness of 6 mm to 12 mm cut from sheetsusing a ASTM standard hole drill. The abrasion loss is measured usingMethod B of ASTM D 5963-97a on a Gotech GT-7012-D abrasion test machine.The tests are performed at 22 degrees C. with an abrasion path of 40meters. The sample is abraded with VSM-VITEX-KK511X-60P sandpaper(commercially available from VSM Abrasives Corp.), using an abrasionload of 10 Newton. The mass and/or volume of the sample is measuredbefore and after the test, with the difference being the abrasion loss.The smaller the abrasion loss, the better the abrasion resistance of thematerial.

Solid Polymer Coefficient of Friction Test (Wet & Dry)

This test measures the coefficient of friction of the Coefficient ofFriction Test for a sample (e.g., taken with the above-discussedComponent Sampling Procedure, Plaque Sampling Procedure, or the NeatSampling Procedure). The sample is cut into a rectangular shapemeasuring approximately 3.0 inches by 3.3 inches, and having a thicknessof about 2 millimeters. The sample is permanently adhered to a 1centimeter thick piece of EVA foam having a density of approximately0.25 grams/cubic centimeters and having a Durometer hardness of 50 C.

For a dry test (i.e., to determine a dry-state coefficient of friction),the sample is initially equilibrated at 25 degree C. and 20 percenthumidity for 24 hours. For a wet test (i.e., to determine a wet-statecoefficient of friction), the sample is fully immersed in a deionizedwater bath maintained at 25 degree C. for 24 hours. After that, thesample is removed from the bath and blotted with a cloth to removesurface water.

The measurement is performed with an aluminum sled mounted on a testtrack, which is used to perform a sliding friction test for test sampleon the surface of the test track. The surface of the test track mayinclude a specified test track material, such as aluminum, wood courtsurface (wet or dry), smooth concrete surface (wet or dry). The testtrack measures 127 millimeters wide by 610 millimeters long. Thealuminum sled measures 76.2 millimeters by 76.2 millimeters, with a 9.5millimeter radius cut into the leading edge. The contact area of thealuminum sled with the track is 76.2 millimeters by 66.6 millimeters, or5,100 square millimeters).

The dry or wet sample is attached to the bottom of the sled using a roomtemperature-curing two-part epoxy adhesive commercially available underthe tradename “LOCTITE 608” from Henkel, Dusseldorf, Germany. Theadhesive is used to maintain the planarity of the wet sample, which cancurl when saturated. A polystyrene foam having a thickness of about 25.4millimeters is attached to the top surface of the sled (opposite of thetest sample) for structural support.

The sliding friction test is conducted using a screw-driven load frame.A tow cable is attached to the sled with a mount supported in thepolystyrene foam structural support, and is wrapped around a pulley todrag the sled across the aluminum test track. The sliding or frictionalforce is measured using a load transducer with a capacity of 2,000Newtons. The normal force is controlled by placing weights on top of thealuminum sled, supported by the foam structural support, for a totalsled weight of 1000 Newtons). The crosshead of the test frame has aspeed of 0.4 meters/second, and the total test displacement is 250millimeters. The coefficient of friction is calculated based on thesteady-state force parallel to the direction of movement required topull the sled at constant velocity. The coefficient of friction itselfis found by dividing the steady-state pull force by the applied normalforce. Any transient value relating static coefficient of friction atthe start of the test is ignored.

Ply Adhesion Testing

Ply adhesion testing determines the adhesion between two bonded plies ofmaterial (e.g., a thermoplastic copolyester composition and a secondpolymeric material) using a tensile testing device such as an InstronElectropuls E10000 (Instron, Norwood, Mass., USA). Sample plies of eachmaterial may be provided using the Neat Sampling Procedure or the PlaqueSampling Procedure or Component Sampling Procedure, and the plies arethereafter bonded using a specified method. Alternatively, a sample ofbonded plies may be provided by using the Component Sampling Procedure.On one end of the sample, the bond between the plies is carefullyseparated to provide approximately 0.5 centimeter unbonded length thatmay be inserted into the crossheads of the tensile testing device. Afirst ply is inserted into a first grip of the tensile tester, and asecond ply is inserted into a second grip of the tensile tester so thatthe sample between the grips is substantially straight. The crossheadspeed is set to 50 millimeters per minute. The peel strength is measuredthroughout the separation of the bonded sample until the bond fullyseparates or the sample fails. The force per peel distance is reported(kilograms force/centimeter), and the mode of failure (either adhesiveor cohesive) is recorded for each sample.

Foam Characterization.

Density Test

The density is measured for samples taken using the Plaque SamplingProcedure, or the Component Sampling Procedure, using a digital balanceor a Densicom Tester (Qualitest, Plantation, Fla., USA). For each samplea sample volume is determined in cubic centimeters, and then each sampleis weighed (g). The density of the sample is the mass divided by thesample volume, given in grams/cubic centimeters.

Specific Gravity Test

The specific gravity (SG) is measured for samples taken using the PlaqueSampling Procedure, or the Component Sampling Procedure, using a digitalbalance or a Densicom Tester (Qualitest, Plantation, Fla., USA). Eachsample is weighed (g) and then is submerged in a distilled water bath(at 22 degrees C. plus or minus 2 degrees C.). To avoid errors, airbubbles on the surface of the samples are removed, e.g., by wipingisopropyl alcohol on the sample before immersing the sample in water, orusing a brush after the sample is immersed. The weight of the sample inthe distilled water is recorded. The specific gravity is calculated withthe following formula:

${S.G.} = \frac{{Weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {sample}\mspace{14mu} {in}\mspace{14mu} {air}\mspace{14mu} (g)}{\begin{matrix}{{{Weight}\mspace{14mu} {of}\mspace{14mu} {sample}\mspace{14mu} {in}\mspace{14mu} {air}\mspace{14mu} (g)} -} \\{{Weight}\mspace{14mu} {of}\mspace{14mu} {sample}\mspace{14mu} {in}\mspace{14mu} {water}\mspace{14mu} (g)}\end{matrix}}$

Water Uptake Test

This test measures the water uptake capacity of a foam sample after asoaking duration of 5 minutes. A 1-centimeter core sample is removedfrom a foam sample prepared using the Plaque Sampling Procedure orComponent Sampling Procedure, starting from the side wall of the foamedarticle, e.g., the midsole of an article of footwear. The core is thencut to provide a cylindrical sample having a 1-centimeter cylinderheight, ensuring that the side wall remains as part of the core sample.The sample is conditioned in an oven for 24 hours at 50 degrees C. plusor minus 3 degrees C. After conditioning, the sample is cooled for 30minutes in a lab environment at a temperature of 22 degrees C. plus orminus 2 degrees C., and then is immediately weighed, and the weightrecorded in grams (W_0). The surface of the side wall is masked withmasking tape, while all other surfaces are sealed with a nonpermeablecoating. When the surfaces are fully coated, the sidewall surface isunmasked. The coated sample is then conditioned in an oven for 24 hoursat 50 degrees C. plus or minus 3 degrees C., cooled for 30 minutes in alab environment at a temperature of 22 degrees C. plus or minus 2degrees C., and then is immediately weighed and the weight recorded ingrams (W_i). The dried sample is fully immersed in a deionized waterbath maintained at 22 degrees C. plus or minus 2 degrees C., for aduration of 5 minutes. After the soaking duration, the sample is removedfrom the deionized water bath, blotted with a cloth to remove surfacewater, and the total weight of the soaked sample (W_f) is measured ingrams (W_f). The water uptake for the time period is calculated asfollows:

${{Water}\mspace{14mu} {Uptake}\mspace{14mu} {Capacity}} = {\frac{{W\_ f} - {W\_ i}}{W\_ i} \times 100\%}$

Force/Displacement Test (Cyclic Compression Test)

Force/displacement behavior for the foams and the foamed articles ismeasured using samples having a diameter of 45 millimeters and athickness of at least 10 millimeters (preferably 20 to 25 millimeters)prepared using the Plaque Sampling Procedure or the Component SamplingProcedure with a cyclic compression testing device such an InstronElectropuls E10000 (Instron, Norwood, Mass., USA) with a stainless steelcircular cross section impact geometry having a diameter at least twicethe diameter of the foam sample (e.g., for a 45-millimeter diametersample, a 90-millimeter diameter platen). Each sample is compressed to50% strain at 5 Hz for 500 cycles. Stiffness, efficiency, and energyreturn are measured from the force vs. displacement curves for cycles200, 300, 400, and 500. Stiffness of a particular foam sample is thestress at the maximum strain divided by the maximum strain, giving avalue in kPa or N/mm. Efficiency of a foam sample is the integral of theunloading force-displacement curve divided by the integral of theloading force-displacement curve. Energy return of a foam sample is theintegral of the unloading force-displacement curve, giving a value inmJ. The reported value for each metric is the average of each metricbetween cycles 200, 300, 400, and 500. All fatigue metrics are definedas relative differences in properties at the end of the test compared tothe same properties at the beginning of the test (i.e., cycle 1).

In some cases, a full midsole is tested using a footform for impactinstead of a cylindrical tupp to more accurately simulate full gateloading. For these tests, a US mens size 10 midsole is tested, and amens size 9 footform used for impact, with a load of 2000N being appliedto the midsole with the footform at a loading rate of 5 Hz. All of themetrics from the footform test are collected and analyzed as describedabove.

As with when a cylindrical tupp is used, when a footform is used, energyinput is taken as the integral of the force-displacement curve duringcompression force loading. Energy return is taken as the integral of theforce displacement curve during unloading. Hysteresis is taken as theratio: (energy return)/(energy input), which can also be viewed as theenergy efficiency of the foam. Fatigue behavior is judged by changes inthe foam displacement at the max load of a cycle. All measuredproperties: stiffness, hysteresis, and fatigue are measured forthousands of cycles for both running and walking compression cycles.

Durometer Hardness Test—Shore A

The test used to obtain the hardness values for the foam articles is asfollows. A flat foam sample is prepared using the Plaque SamplingProcedure or the Component Sampling Procedure, where the sample has aminimum of 6 mm thick for Shore A durometer testing. If necessary,samples are stacked to make up the minimum thickness. Samples are largeenough to allow all measurements to be performed at a minimum of 12 mmfrom the edge of the sample and at least 12 mm from any othermeasurement. Regions tested are flat and parallel with an area at least6 mm in diameter. A minimum of five hardness measurements are taken andtested using a 1 kilogram head weight.

Split Tear Test

The split tear test can determine the internal tear strength for a foammaterial. A sample may be provided either using the Plaque SamplingProcedure or the Component Sampling Procedure. The sample is die cutinto a rectangular shape having a width of 1.54 centimeters and a lengthof 15.24 centimeters (1 inch by 6 inches), and having a thickness of 10millimeters, plus or minus 1 millimeter. On one end, a cut is made intothe sample that bisects the thickness, the cut extending the full widthof the sample, and 3 centimeters from the end of the sample. Startingfrom the end of the cut, 5 marks are placed along the length of thesample spaced 2 centimeters apart. The cut ends of the sample are placedin the clamps of a tensile tester. Each section of the sample is held ina clamp in such a manner that the original adjacent cut edges form astraight line joining the centers of the clamps. The crosshead speed isset to 50 millimeters per minute. The tear strength is measuredthroughout the separation of the crossheads. If necessary, a sharp knifemay be used to keep separating the foam in the center of the sample,discarding the readings caused by cutting of the knife. The lowest splittear strength values are recorded for each of the five marked segmentsof the sample (between each of the 2-centimeter markings). An averagesplit tear strength value is recorded for each sample. If a segment of asample has an air bubble measuring more than 2 millimeters, the tearstrength for the segment is discarded, and the air bubble recorded as atest defect. If more than one segment of a sample has an air bubblemeasuring more than 2 millimeters, the entire sample is discarded.

Hand Pull Test

The hand pull test can evaluate the bond strength between two foams,compositions or materials, such as between a solid and a foam or betweentwo different foams. Depending upon the bonding method used, a sample oftwo pre-bonded foams, compositions or materials may be provided eitherusing the Plaque Sampling Procedure or the Component Sampling Procedure.Alternatively, separate samples of a foam, a composition or a materialcan be prepared using the Plaque Sampling Procedure or the ComponentSampling Procedure, and then can be bonded together using the bondingmethod to be evaluated. The sample is die cut into a rectangular shapehaving a width of 1.54 centimeters and a length of 15.24 centimeters (1inch by 6 inches), and having a thickness of 10 millimeters, plus orminus 1 millimeter. On one end, a cut is made into the sample thatbisects the thickness, the cut extending the full width of the sample,and 3 centimeters from the end of the sample. Starting from the end ofthe cut, 5 marks are placed along the length of the sample spaced 2centimeters apart. The cut ends of the sample are held in the tester'shand and pulled at a rate of approximately 50 millimeters per minute. Ifnecessary, a sharp knife may be used to keep separating the material inthe center of the sample, discarding the readings caused by cutting ofthe knife. Tear strength values are recorded for each of the five markedsegments of the sample (between each of the 2-centimeter markings),using the following scoring rubric: easy to peel or adhesive failure isgiven a score of 1; an adhesive failure but some resistance is given ascore of 2; cohesive foam failure is given a score of 3 to 4.5 based onthe accompanying level of foam skin failure, where 3 is the highestlevel of foam skin failure and 4.5 is the lowest level of foam skinfailure; and unable to separate is given a score of 5. The scores foreach segment are averaged to give value recorded for each sample. If asegment of a sample has an air bubble measuring more than 2 millimeters,the tear strength for the segment is discarded, and the air bubblerecorded as a test defect. If more than one segment of a sample has anair bubble measuring more than 2 millimeters, the entire sample isdiscarded.

ASPECTS

The following listing of exemplary aspects supports and is supported bythe disclosure provided herein.

Aspect 1. A thermoplastic copolyester composition comprising:

a thermoplastic copolyester comprising,

(a) a plurality of first segments, each first segment derived from adihydroxy-terminated polydiol;(b) a plurality of second segments, each second segment derived from adiol; and(c) a plurality of third segments, each third segment derived from anaromatic dicarboxylic acid.Aspect 2. The thermoplastic copolyester composition of Aspect 1, whereinthe thermoplastic copolyester is a block copolymer; a segmentedcopolymer; a random copolymer; or a condensation copolymer.Aspect 3. The thermoplastic copolyester composition of Aspects 1 or 2,wherein the thermoplastic copolyester has a weight average molecularweight of about 50,000 Daltons to about 1,000,000 Daltons.Aspect 4. The thermoplastic copolyester composition of Aspect 3, whereinthe thermoplastic copolyester has a weight average molecular weight ofabout 50,000 Daltons to about 500,000 Daltons; about 75,000 Daltons toabout 300,000 Daltons; or about 100,000 Daltons to about 200,000Daltons.Aspect 5. The thermoplastic copolyester composition of any one ofAspects 1-4, wherein the thermoplastic copolyester has a ratio of firstsegments to third segments from about 1:1 to about 1:5 based on theweight of each of the first segments and the third segments.Aspect 6. The thermoplastic copolyester composition of Aspect 5, whereinthe thermoplastic copolyester has a ratio of first segments to thirdsegments from about 1:1 to about 1:3 or about 1:1 to about 1:2 based onthe weight of each of the first segments and the third segments.Aspect 7. The thermoplastic copolyester composition of any one ofAspects 1-6, wherein the thermoplastic copolyester has a ratio of secondsegments to third segments from about 1:1 to about 1:3 based on theweight of each of the first segments and the third segments.Aspect 8. The thermoplastic copolyester composition Aspect 7, whereinthe thermoplastic copolyester has a ratio of second segments to thirdsegments from about 1:1 to about 1:2 or about 1:1 to about 1:1.52 basedon the weight of each of the first segments and the third segments.Aspect 9. The thermoplastic copolyester composition of any one ofAspects 1-8, wherein the first segments derived from adihydroxy-terminated polydiol comprise segments derived from apoly(alkylene oxide)diol having a number-average molecular weight ofabout 250 Daltons to about 6000 Daltons.Aspect 10. The thermoplastic copolyester composition of Aspect 9,wherein the number-average molecular weight is about 400 Daltons toabout 6,000 Daltons; about 350 Daltons to about 5,000 Daltons; or about500 Daltons to about 3,000 Daltons.Aspect 11. The thermoplastic copolyester composition of any one ofAspects 9-10, wherein the poly(alkylene oxide)diol is poly(ethyleneether)diol; poly(propylene ether)diol; poly(tetramethylene ether)diol;poly(pentamethylene ether)diol; poly(hexamethylene ether)diol;poly(heptamethylene ether)diol; poly(octamethylene ether)diol;poly(nonamethylene ether)diol; poly(decamethylene ether)diol; ormixtures thereof.Aspect 12. The thermoplastic copolyester composition of Aspect 11,wherein the poly(alkylene oxide)diol is poly(ethylene ether)diol;poly(propylene ether)diol; poly(tetramethylene ether)diol;poly(pentamethylene ether)diol; or poly(hexamethylene ether)diol.Aspect 13. The thermoplastic copolyester composition of Aspect 11,wherein the poly(alkylene oxide)diol is poly(tetramethylene ether)diol.Aspect 14. The thermoplastic copolyester composition of any one ofAspects 1-13, wherein the second segments derived from a diol comprise adiol having a molecular weight of less than about 250.Aspect 15. The thermoplastic copolyester composition of Aspect 14,wherein the diol is a C2-C8 diol.Aspect 16. The thermoplastic copolyester composition of Aspect 15,wherein the second segments derived from a diol comprise a diol selectedfrom ethanediol; propanediol; butanediol; pentanediol; 2-methylpropanediol; 2,2-dimethyl propanediol; hexanediol; 1,2-dihydroxycyclohexane; 1,3-dihydroxy cyclohexane; 1,4-dihydroxy cyclohexane; andmixtures thereof.Aspect 17. The thermoplastic copolyester composition of Aspect 16,wherein the diol is selected from 1,2-ethanediol, 1,3-propanediol,1,4-butanediol, 1,6-hexanediol, and mixtures thereof.Aspect 18. The thermoplastic copolyester composition of any one ofAspects 1-17, wherein the third segments derived from an aromaticdicarboxylic acid comprise an aromatic C5-C16 dicarboxylic acid.Aspect 19. The thermoplastic copolyester composition of Aspect 18,wherein the aromatic C5-C16 dicarboxylic acid has a molecular weightless than about 300 Daltons or about 120 Daltons to about 200 Daltons.Aspect 20. The thermoplastic copolyester composition of Aspect 18,wherein the aromatic C5-C16 dicarboxylic acid is terephthalic acid,phthalic acid, isophthalic acid, or a derivative thereof.Aspect 21. The thermoplastic copolyester composition of Aspect 20,wherein the aromatic C5-C16 dicarboxylic acid is terephthalic acid orthe dimethyl ester derivative thereof.Aspect 22. The thermoplastic copolyester composition of any one ofAspects 1-21, wherein the thermoplastic copolyester comprises,

-   -   (a) a plurality of first copolyester units, each first        copolyester unit of the plurality comprising the first segment        derived from a dihydroxy-terminated polydiol and the third        segment derived from an aromatic dicarboxylic acid, wherein the        first copolyester unit has a structure represented by a formula        1:

wherein R₁ is a group remaining after removal of terminal hydroxylgroups from the poly(alkylene oxide) diol of the first segment, whereinthe poly(alkylene oxide) diol of the first segment is a poly(alkyleneoxide) diol having a number-average molecular weight of about 400 toabout 6000; and wherein R₂ is a group remaining after removal ofcarboxyl groups from the aromatic dicarboxylic acid of the thirdsegment; and

-   -   (b) a plurality of second copolyester units, each second        copolyester unit of the plurality comprising the second segment        derived from a diol and the third segment derived from an        aromatic dicarboxylic acid, wherein the second copolyester unit        has a structure represented by a formula 2:

wherein R₃ is a group remaining after removal of hydroxyl groups fromthe diol of the second segment derived from a diol, wherein the diol isa diol having a molecular weight of less than about 250; and wherein R₂is the group remaining after removal of carboxyl groups from thearomatic dicarboxylic acid of the third segment.Aspect 23. The thermoplastic copolyester composition of Aspect 22,wherein the first copolyester unit has a structure represented by aformula 3:

wherein R is H or methyl; wherein y is an integer having a value from 1to 10; wherein z is an integer having a value from 2 to 60; and whereina weight average molecular weight of each of the plurality of firstcopolyester units is from about 300 Daltons to about 7,000 Daltons.Aspect 24. The thermoplastic copolyester composition of Aspect 23,wherein y is an integer having a value of 1, 2, 3, 4, or 5.Aspect 25. The thermoplastic copolyester composition of Aspect 23 or 24,wherein R is hydrogen; wherein R is methyl; wherein R is hydrogen and yis an integer having a value of 1, 2, or 3; or wherein R is methyl and yis an integer having a value of 1.Aspect 26. The thermoplastic copolyester composition of Aspect 22,wherein the first copolyester unit has a structure represented by aformula 4:

wherein z is an integer having a value from 2 to 60; and wherein aweight average molecular weight of each of the plurality of firstcopolyester units is from about 300 Daltons to about 7,000 Daltons.Aspect 27. The thermoplastic copolyester composition of any one ofAspects 23-26, wherein z is an integer having a value from 5 to 60; from5 to 50; from 5 to 40; from 4 to 30; from 4 to 20; or from 2 to 10.Aspect 28. The thermoplastic copolyester composition of any one ofAspects 23-27, wherein the weight average molecular weight of each ofthe plurality of first copolyester units is from about 400 Daltons toabout 6,000 Daltons; from about 400 Daltons to about 5,000 Daltons; fromabout 400 Daltons to about 4,000 Daltons; from about 400 Daltons toabout 3,000 Daltons; from about 500 Daltons to about 6,000 Daltons; fromabout 500 Daltons to about 5,000 Daltons; from about 500 Daltons toabout 4,000 Daltons; from about 500 Daltons to about 3,000 Daltons; fromabout 600 Daltons to about 6,000 Daltons; from about 600 Daltons toabout 5,000 Daltons; from about 600 Daltons to about 4,000 Daltons; fromabout 600 Daltons to about 3,000 Daltons.Aspect 29. The thermoplastic copolyester composition of any one ofAspects 22-28, wherein the second copolyester unit has a structurerepresented by a formula 5:

wherein x is an integer having a value from 1 to 20.Aspect 30. The thermoplastic copolyester composition of Aspect 29,wherein x is an integer having a value from 2 to 18; a value from 2 to17; a value from 2 to 16; a value from 2 to 15; a value from 2 to 14; avalue from 2 to 13; a value from 2 to 12; a value from 2 to 11; a valuefrom 2 to 10; a value from 2 to 9; a value from 2 to 8; a value from 2to 7; a value from 2 to 6; or a value of 2, 3, or 4.Aspect 31. The thermoplastic copolyester composition of Aspect 29,wherein the second copolyester unit has a structure represented by aformula 6:

Aspect 32. The thermoplastic copolyester composition of any one ofAspects 22-31, wherein the thermoplastic copolyester comprises a weightpercent of the plurality of first copolyester units based on totalweight of the thermoplastic copolyester of about 30 weight percent toabout 80 weight; about 40 weight percent to about 80 weight percent;about 50 weight percent to about 80 weight percent; about 30 weightpercent to about 70 weight percent; about 40 weight percent to about 70weight percent; or about 50 weight percent to about 70 weight percent.Aspect 33. The thermoplastic copolyester composition of any one ofAspects 22-32, wherein the thermoplastic copolyester comprises a weightpercent of the plurality of second copolyester units based on totalweight of the thermoplastic copolyester of about 40 weight percent toabout 65 weight percent; about 45 weight percent to about 65 weightpercent; about 50 weight percent to about 65 weight percent; about 55weight percent to about 65 weight percent; about 40 weight percent toabout 60 weight percent; about 45 weight percent to about 60 weightpercent; about 50 weight percent to about 60 weight percent; or about 55weight percent to about 60 weight percent.Aspect 34. The thermoplastic copolyester composition of any one ofAspects 1-33, wherein the thermoplastic copolyester composition furthercomprises an additive.Aspect 35. The thermoplastic copolyester composition of Aspect 34,wherein the additive is present in an amount from about 0.1 weightpercent to about 10 weight percent based on the total weight of thefoamed polymeric material.Aspect 36. The thermoplastic copolyester composition of Aspects 34 or35, wherein the additive is a wax, an anti-oxidant, a UV-absorbingagent, a coloring agent, or combinations thereof.Aspect 37. The thermoplastic copolyester composition of any one ofAspects 1-36, wherein the thermoplastic copolyester composition furthercomprises a filler.Aspect 38. The thermoplastic copolyester composition e of Aspect 37,wherein the filler is present in an amount from about 0.05 weightpercent to about 20 weight percent or from about 0.1 weight percent toabout 10 weight percent based on the total weight of the foamedpolymeric material.Aspect 39. The thermoplastic copolyester composition of any one ofAspect 37 or 38, wherein the filler is a particulate filler; or whereinthe filler is a carbonaceous filler.Aspect 40. The thermoplastic copolyester composition of Aspect 39,wherein the carbonaceous filler is carbon black, activated carbon,graphite, carbon fibers, carbon fibrils, carbon nanoparticles, orcombinations thereof; and wherein the carbonaceous filler is optionallychemically-modified.Aspect 41. The thermoplastic copolyester composition of Aspect 37,wherein the filler is an inorganic filler.Aspect 42. The thermoplastic copolyester composition of Aspect 41,wherein the inorganic filler is an oxide, a hydroxide, a salt, asilicate, a metal, or combinations thereof; or wherein the inorganicfiller comprises glass spheres, glass fibers, glass hollow spheres,glass flakes, MgO, SiO₂, Sb₂O₃, Al₂O₃, ZnO, talc, mica, kaolin,wollastonite, or combinations thereof.Aspect 43. The thermoplastic copolyester composition of any one ofAspects 37-41, wherein the filler is present in an amount for from about0.1 weight percent to less than about 15 weight percent.Aspect 44. The thermoplastic copolyester composition of Aspect 43,wherein the filler is present in an amount for from about 0.1 weightpercent to about 10 weight percent.Aspect 45. The thermoplastic copolyester composition of Aspect 43,wherein the filler is present in an amount for from about 0.1 weightpercent to about 7.5 weight percent.Aspect 46. The thermoplastic copolyester composition of Aspect 43,wherein the filler is present in an amount for from about 0.1 weightpercent to about 5 weight percent.Aspect 47. The thermoplastic copolyester composition of Aspect 43,wherein the filler is present in an amount for from about 0.1 weightpercent to about 4 weight percent.Aspect 48. The thermoplastic copolyester composition of any one ofAspects 1-48, wherein the thermoplastic copolyester composition consistsessentially of one or more thermoplastic copolyester.Aspect 49. The thermoplastic copolyester composition of any one ofAspects 1-48, further comprising at least one ionomer.Aspect 50. The thermoplastic copolyester composition of any one ofAspects 1-48, further comprising at least one thermoplasticpolyurethane.Aspect 51. The thermoplastic copolyester composition of any one ofAspects 1-50, wherein the thermoplastic copolyester composition issubstantially free of a thermoplastic polyamide polymer, includepolyamide copolymers such as polyether block amide copolymers.Aspect 52. The thermoplastic copolyester composition of any one ofAspects 1-50, wherein the thermoplastic copolyester composition issubstantially free of a thermoplastic polyolefin polymers, includingpolyethylene and polypropylene and/or polyolefin copolymers such asethylene-vinyl acetate copolymers.Aspect 53. The thermoplastic copolyester composition of any one ofAspects 1-52, wherein the thermoplastic copolyester has a zero shearviscosity when determined using a cyclic tensile test as describedherein of about 10 to about 10,000 pascal-second; about 100 to about7,000 pascal-second; or about 1,000 to about 5,000 pascal-second.Aspect 54. A method for making a foam article, the method comprising:forming a mixture of molten polymeric material comprising athermoplastic elastomer and a blowing agent;injecting the mixture into a mold cavity;foaming the molten polymeric material, thereby forming a foamed moltenpolymeric material;solidifying the foamed molten polymeric material, thereby forming a foamarticle having a multicellular foam structure; andremoving the foam article from the mold cavity.Aspect 55. The method of Aspect 54, wherein the thermoplastic elastomeris a thermoplastic copolyester of any one of Aspects 1-53.Aspect 56. The method of Aspect 54 or 55, wherein the blowing agent is aphysical blowing agent.Aspect 57. The method of Aspect 56, wherein the physical blowing agentis a supercritical fluid.Aspect 58. The method of Aspect 57, wherein the supercritical fluidcomprises nitrogen, or a supercritical fluid thereof.Aspect 59. The method of Aspect 58, wherein the supercritical fluidcomprises or consists essentially of nitrogen, or a supercritical fluidthereof.Aspect 60. The method of Aspect 58, wherein the supercritical fluidfurther comprises carbon dioxide, or a supercritical fluid thereof.Aspect 61. The method of Aspect 60, wherein the carbon dioxide ispresent in an amount of about 1% to about 3% or about 1% to about 5% byweight based on upon a total weight of the mixture.Aspect 62. The method of any one of Aspects 58-61, wherein the nitrogenis present in an amount of about 1% to about 3% or about 1% to about 5%by weight based on upon a total weight of the mixture.Aspect 63. The method of any one of Aspects 55-61, wherein the formingthe mixture of the molten polymeric material and the physical blowingagent comprises adding the physical blowing agent to the molten polymermaterial and forming a single phase solution of the physical blowingagent dissolved in the molten polymer material.Aspect 64. The method of any one of Aspects 55-61, wherein the formingthe mixture of the molten polymer material and the physical blowingagent comprises infusing a solid resin comprising the polymeric materialwith the physical blowing agent to form infused resin, and melting theinfused resin to form a single phase solution of the physical blowingagent dissolved in the molten polymeric mixture.Aspect 65. The method of any one of Aspects 55-64, wherein the injectingthe mixture into the mold cavity comprises injecting the mixture into apressurized mold cavity, the pressurized mold cavity having a firstpressure greater than atmospheric pressure; and the foaming the moltenpolymeric material comprises decreasing the first pressure to a secondpressure and initiating formation of gas bubbles by the physical blowingagent, thereby foaming the molten polymeric material.Aspect 66. The method of any one of Aspects 63-65, wherein the injectingthe mixture into the mold cavity comprises injecting the mixture into apressurized mold cavity having a first pressure greater than atmosphericpressure.Aspect 67. The method of Aspect 66, wherein the method comprisesapplying a gas counter pressure to the mold cavity of from about 100 psito about 3,000 psi, or from about 550 psi to about 1500 psi, or fromabout 650 psi to about 1000 psi, and wherein the gas counter pressure isapplied to the mold cavity before the foaming.Aspect 68. The method of Aspect 65, wherein the second pressure isatmospheric pressure; and wherein decreasing the first pressure to thesecond pressure comprises venting the pressurized mold cavity toatmospheric pressure.Aspect 69. The method of Aspect 65, wherein the second pressure isatmospheric pressure; and wherein decreasing the first pressure to thesecond pressure comprises using a controlled rate of pressure decreaseuntil the mold cavity has a pressure essentially equal to atmosphericpressure.Aspect 70. The method of Aspect 65, wherein the controlled rate ofpressure decrease is from about 10 psi per sec to about 600 psi per sec,or from about 15 psi per sec to about 300 psi per sec, or from about 20psi per sec to about 150 psi per sec.Aspect 71. The method of Aspect 65, wherein the second pressure isatmospheric pressure; and wherein decreasing the first pressure to asecond pressure comprises decreasing the pressure in a plurality of stepdecreases in pressure until the mold cavity has a pressure essentiallyequal to atmospheric pressure.Aspect 72. The method of Aspect 54, wherein the blowing agent is achemical blowing agent.Aspect 73. The method of Aspect 72, wherein the chemical blowing agentis present in an amount from about 0.05 weight percent to about 25weight percent or about 0.1 weight percent to about 10 weight percentbased on the total weight of the polymeric mixture.Aspect 74. The method of Aspect 72 or 73, wherein the chemical blowingis an azo compound.Aspect 75. The method of any one of Aspects 54-74, wherein the foamarticle is substantially free of a chemical blowing agent or adecomposition product thereof.Aspect 76. The method of any one of Aspects 54-74, wherein the foamarticle is substantially free of a physical blowing agent.Aspect 77. The method of Aspect 54, wherein the blowing agent comprisesa combination of a physical blowing agent and a chemical blowing agent.Aspect 78. The method of any one of Aspects 54-77, wherein the mixturehas an injection temperature; and wherein the injection temperature isfrom about the melting temperature of the thermoplastic elastomer toabout 50 degrees C. above the tail temperature of the thermoplasticelastomer.Aspect 79. The method of Aspect 78, wherein the injection temperature isfrom about the melting temperature of the thermoplastic elastomer to atemperature that is above the tail temperature of the thermoplasticelastomer by about 0 degrees C., 5 degrees C., 10 degrees C., 15 degreesC., 20 degrees C., 25 degrees C., 30 degrees C., 35 degrees C., 40degrees C., 45 degrees C., or 50 degrees C.Aspect 80. The method of any one of Aspects 54-79, wherein the foamingoccurs at a foaming temperature; and wherein the foaming temperature isfrom about the melting temperature of the thermoplastic elastomer toabout 50 degrees C. above the tail temperature of the thermoplasticelastomer.Aspect 81. The method of Aspect 80, wherein the foaming temperature isfrom about the melting temperature of the thermoplastic elastomer to atemperature that is above the tail temperature of the thermoplasticcopolyester by about 0 degrees C., 5 degrees C., 10 degrees C., 15degrees C., 20 degrees C., 25 degrees C., 30 degrees C., 35 degrees C.,40 degrees C., 45 degrees C., or 50 degrees C.Aspect 82. The method of any one of Aspects 54-81, wherein the foamarticle is a thermoplastic foam article.Aspect 83. The method of any one of Aspects 54-82, wherein themulticellular foam structure is a closed cell foam structure.Aspect 84. The method of any one of Aspects 54-82, wherein themulticellular foam structure is an open cell foam structure.Aspect 85. The method of any one of Aspects 54-84, wherein themulticellular foam has an average cell size of from about 50 micron toabout 5 millimeters; from about 100 micron to about 1 millimeters; orfrom about 50 micron to about 1 millimeters.Aspect 86. The method of any one of Aspects 54-84, wherein thethermoplastic elastomer does not form crosslinks during foaming; orwherein the thermoplastic elastomer does not form crosslinks duringsolidifying.Aspect 87. The method of any one of Aspects 54-86, wherein thesolidifying comprises cooling the mold cavity; or wherein thesolidifying comprises cooling the foamed molten polymeric material.Aspect 88. The method of any one of Aspects 54-87, wherein the foamingcomprises releasing pressure from the mold cavity at a mold cavitypressure release rate.Aspect 89. The method of Aspect 88, wherein the mold cavity pressurerelease rate is about 10 psi per sec to about 600 psi per sec, or about15 psi per sec to about 300 psi per sec, or about 20 psi per sec toabout 150 psi per sec.Aspect 90. The method of any one of Aspects 54-87, wherein the foamingcomprises providing a gas counter pressure to the mold cavity.Aspect 91. The method of Aspect 90, wherein the gas counter pressure isat least about 550 psi, about 550 psi to about 1500 psi, or about 650psi to about 1000 psi.Aspect 92. The method of Aspect 91, wherein the blowing agent is aphysical blowing agent; or wherein the blowing agent is supercriticalnitrogen.Aspect 93. The method of any one of Aspects 54-92, the method furthercomprising placing a textile element in the mold cavity prior toinjecting the mixture, and foaming the molten polymeric material incontact with the textile element.Aspect 94. The method of Aspect 93, wherein the textile elementcomprises thermoplastic polyester fibers, thermoplastic polyester yarns,thermoplastic polyurethane fibers, thermoplastic polyurethane yarns,thermoplastic polyamide fibers, thermoplastic polyamide yarns, orcombinations thereof.Aspect 95. The method of Aspects 93 or 94, wherein the textile elementis a component for an upper for an article of footwear.Aspect 96. The method of any one of Aspects 54-95, wherein the foamarticle is a component of an article of footwear.Aspect 97. The method of Aspect 96, wherein the foam article is amidsole.Aspect 98. The method of any one of Aspects 54-95, wherein the foamarticle is a component of an article of apparel.Aspect 99. The method of any one of Aspects 54-95, wherein the foamarticle is a component of an article of sporting equipment.Aspect 100. The method of any one of Aspects 54-99, wherein theinjecting comprises monitoring an injection pressure of the mixtureprior or during the injecting, and controlling the injecting based onthe injection pressure of the mixture.Aspect 101. The method of any one of Aspects 54-100, wherein theinjecting comprises controlling the injection temperature of the mixtureprior to the mixture entering the mold cavity.Aspect 102. The method of any one of Aspects 54-101, wherein theinjecting comprises controlling a mold cavity temperature prior to themixture entering the mold cavity.Aspect 103. The method of any one of Aspects 54-102, wherein the mixturehas an expansion ratio of 1 as compared to a volume of the mold cavity.Aspect 104. The method of any one of Aspects 54-103, wherein, followingremoving the foam article from the mold cavity, cooling the foam articleto about 25 degrees C., and equilibrating the foam article at about 25degrees C. and about 1 atm of pressure, a volume of the equilibratedfoam article is within plus or minus 5 percent of a volume of the moldcavity.Aspect 105. The method of any one of Aspects 54-104, wherein themulticellular foam structure has a closed cell foam microstructure.Aspect 106. The method of any one of Aspects 54-105, wherein themulticellular foam structure has an open cell foam microstructure.Aspect 107. The method of Aspect 106, wherein the multicellular foamstructure comprises less than 10 percent of cells having a closed cellmicrostructure.Aspect 108. The method of Aspect 106, wherein the multicellular foamstructure comprises less than 5 percent of cells having a closed cellmicrostructure.Aspect 109. The method of Aspect 106, wherein the multicellular foamstructure comprises less than 1 percent of cells having a closed cellmicrostructure.Aspect 110. The method of any one of Aspects 54-109, wherein themulticellular foam structure has an average cell size of from about 50micron to about 5 millimeters; from about 100 micron to about 1millimeters; or from about 50 micron to about 1 millimeters.Aspect 111. The method of any one of Aspects 54-110, wherein the foamarticle has a maximum load of about 100 N to about 4000 N whendetermined using the Cyclic Tensile test as described herein.Aspect 112. The method of Aspect 111, wherein the foam article has amaximum load of about 100 N to about 4000 N when determined using theCyclic Tensile test as described herein.Aspect 113. The method of any one of Aspects 54-112, wherein the foamarticle has an energy efficiency of greater than or equal to about 50percent when determined using the Cyclic Compression test as describedherein.Aspect 114. The foam article of Aspect 113, wherein the foam article hasan energy efficiency of greater than or equal to about 60 percent whendetermined using the Cyclic Compression test as described herein.Aspect 115. The method of Aspect 113, wherein the foam article has anenergy efficiency of greater than or equal to about 70 percent whendetermined using the Cyclic Compression test as described herein.Aspect 116. The method of Aspect 113, wherein the foam article has anenergy efficiency of about 50 percent to about 97 percent whendetermined using the Cyclic Compression test as described herein.Aspect 117. The method of any one of Aspects 54-116, wherein the foamarticle has an energy return of about 200 millijoules (mJ) to 1200 mJwhen determined using the Cyclic Compression test as described herein.Aspect 118. The method of Aspect 117, wherein the foam article has anenergy return of about 400 mJ to 1000 mJ when determined using theCyclic Compression test as described herein.Aspect 119. The method of Aspect 117, wherein the foam article has anenergy return of about 600 mJ to 800 mJ when determined using the CyclicCompression test as described herein.Aspect 120. The method of any one of Aspects 54-119, wherein the foamarticle has a split tear value of about 1.0 kilogram per centimeter to4.5 kilogram per centimeter, about 1.6 kilogram per centimeter to 4.0kilogram per centimeter, about 2.0 kilogram per centimeter to 4.0kilogram per centimeter, about 2.0 kilogram per centimeter to 3.5kilogram per centimeter, about 2.5 kilogram per centimeter to 3.5kilogram per centimeter, about 0.07 kilogram per centimeter to 2.0kilogram per centimeter, or about 0.8 kilogram per centimeter to 1.5kilogram per centimeter, or about 0.9 to 1.2 kilogram per centimeter,about 1.5 kilogram per centimeter to 2.2 kilogram per centimeter; about0.08 kilogram per centimeter to 4.0 kilogram per centimeter, about 0.9kilogram per centimeter to 3.0 kilogram per centimeter, about 1.0 to 2.0kilogram per centimeter, about 1.0 kilogram per centimeter to 1.5kilogram per centimeter, or about 2 kilogram per centimeter using asplit tear test as described herein.Aspect 121. The method of any one of Aspects 54-120, wherein the foamarticle has a split tear value of greater than or equal to about 1.5kg/cm, greater than or equal to about 2.0 kg/cm, or greater than orequal to about 2.5 kg/cm, when determined using a split tear test asdescribed herein.Aspect 122. The method of any one of Aspects 54-121, wherein the foamarticle has a specific gravity of less than or equal to 0.9.Aspect 123. The foam article of Aspect 122, wherein the foam article hasa specific gravity of from about 0.02 to about 0.22; of from about 0.03to about 0.12; from about 0.04 to about 0.10; from about 0.11 to about0.12; from about 0.10 to about 0.12; from about 0.15 to about 0.2; 0.15to about 0.30; 0.01 to about 0.10; from about 0.02 to about 0.08; fromabout 0.03 to about 0.06; 0.08 to about 0.15; from about 0.10 to about0.12; from about 0.15 to about 0.2; from about 0.10 to about 0.12; fromabout 0.1 to about 0.35; from about 0.12 to about 0.20; from 0.02 toabout 0.22; from about 0.02 to about 0.20; from about 0.02 to about0.18; or from of about 0.02 to about 0.16.Aspect 124. The method of any one of Aspects 54-123, wherein the foamarticle has a stiffness of about 200 kilopascals to about 1000kilopascals, for a cylindrical sample having a diameter of about 45millimeters as determined using the Cyclic Compression Test.Aspect 125. The method of Aspect 124, wherein the foam article has astiffness of about 400 kilopascals to about 900 kilopascals, for acylindrical sample having a diameter of about 45 millimeters asdetermined using the Cyclic Compression Test.Aspect 126. The method of any one of Aspects 54-125, wherein the foamarticle has a change in displacement at max loading of about 1millimeters to about 5 millimeters when measured on foam slabs having athickness of about 1 centimeter, wherein the foam slabs are compressedfor about 5000 cycles of compression from 0 newtons to 300 newtons andback to 0 N per cycle, using a 45 mm diameter cylindrical tupp as thecompression head.Aspect 127. The method of any one of Aspects 54-126, wherein the foamarticle has a change in displacement at max loading of about 2millimeters to about 4 millimeters when measured on foam slabs having athickness of about 1 centimeters, wherein the foam slabs are compressedfor about 5000 cycles of compression from 0 newtons to 300 newtons andback to 0 newtons per cycle, using a 45 mm diameter cylindrical tupp asthe compression head.Aspect 128. The method of any one of Aspects 54-127, further comprisingdisposing a layer comprising a second polymeric material on an exteriorsurface of the foam article.Aspect 129. The method of Aspect 128, further comprising a step ofremoving the foam article from the mold cavity following the disposingstep.Aspect 130. The method of Aspect 128, further comprising a step ofremoving the foam article from the mold cavity before the disposingstep.Aspect 131. The method of any one of Aspects 128-130, wherein the secondpolymeric material comprises a thermoplastic elastomer or thermoplasticvulcanizate material for use a type of ground contact, reinforcing skin,containment layer, outsole, rand, or other application.Aspect 132. The method of any one of Aspects 128-131, wherein the secondpolymer material comprises a thermoplastic elastomer (TPE) from polymerchemical families such as copolyesters, thermoplastic polyurethanes(TPU), styrenic copolymers like styrene butadiene rubbers (SBRs),styrene ethylene butadiene styrene (SEBSs), styrene ethylene propylenestyrene (SEPS), ethylenic copolymers such as ethylene-propylenecopolymers, olefinic block copolymers, Surlyns and other ionomers,and/or acrylic copolymer elastomers wherein they are block copolymerscomprised of PMMA blocks—acrylate blocks—PMMA blocks, etc,Aspect 133. The method of any one of Aspects 128-132, wherein the secondpolymer material is comprised of an injection processible thermoplasticvulcanizate (TPV) material, which are typically cross-linked orpartially cross-linked rubbers dispered into thermoplastic host phases,such as an ethylene propylene diene rubber in polypropylene (EPDM/PP)where examples include Sarlink or Santoprene TPV tradenames, or alkylacrylic copolymer rubbers in polyamide hosts (ACM/PA) where examplesinclude Zeotherm TPVs, or silicone rubbers dispersed in Hytrel basedcopolyesters (e.g. so called TSiPVs)Aspect 134. The method of any one of Aspects 128-133, wherein the secondmaterial if used as a solid polymer material without the addition ofcompressed gas, supercritical fluid or other blowing agent has adurometer less than Shore A 90, optionally less than Shore A 85, andpreferably less than Shore A 80, but greater than Shore A 60, andoptionally greater than Shore A 65.Aspect 135. The method of any one of Aspects 128-134, wherein the secondmaterial if used as a solid polymer is comprised of TPEs or TPVs withdensities less than 1.25 g/cc, optionally less than 1.1 g/cc, or lessthan 0.95 g/cc and preferably less than 0.9 g/cc.Aspect 136. The method of any one of Aspects 128-135, wherein the secondpolymer material is produced separately via injection molding with orwithout the addition of compressed gas, supercritical fluids or otherblowing agents upon which the foam article is produced or injected viaovermolding.Aspect 137. The method of any one of Aspects 128-136, wherein the secondmaterial (TPE or TPV) is extruded into a fused deposition 3D printingfilament of 1.5 mm, 1.75 mm, 1.85 mm, 2.85 mm 3.0 mm, or other relevantdiameter for deposition and attachment to foamed article comprised ofthe first material in such a way that it comprises the ground contactlayer, print-on outsole, or other exterior features. Any grade commonlyused in injection molding will typically suffice for 3D print filamentfor fused deposition applications.Aspect 138. The method of Aspect 137, wherein the second material wasproduce via sequential injection in the same process, or wherein thesecond material was produced in a separate process, and subsequentlyinserted into the mold after which foam article from the first materialis overvmolded.Aspect 139. The method of any one of Aspects 128-138, wherein the secondpolymer material is produced separately via injection molding with onlysufficient compressed gas, supercritical fluids or other blowing agentsto achieve a density of 0.9 g/cc or less, 0.85 g/cc or less, or 0.8 g/ccor less.Aspect 140. The method of any one of Aspects 128-139, wherein the secondpolymer materials is a film or an outsole or a rand that is pretreatedwith a plasma or corona treatment prior to receiving an overmoldingassembly method.Aspect 141. The method of any one of Aspects 128-140, wherein the secondpolymer material is a film or an outsole or a rand that is pretreatedwith a primer alone, or a primer plus and an adhesive prior to receivingthe overmolding assembly method described in Aspects above.Aspect 142. The method of any one of Aspects 128-141, wherein the plyadhesion strength between the second polymer material and the firstpolymer material comprising overmolded foam article exceeds 2.5 kilogramforce per centimeter.Aspect 143. The method of Aspect 142, wherein the ply adhesion strengthbetween the second polymer material and the first polymer materialcomprising the foam article exceeds 3.0 kilogram force per centimeter.Aspect 144. The method of any one of Aspects 54-143, wherein the foamarticle comprises greater than about 90 weight percent of thethermoplastic copolyester based on the total weight of the thermoplasticelastomer composition.Aspect 145. The method of Aspect 144, wherein the foam article comprisesgreater than about 95 weight percent of the thermoplastic copolyesterbased on the total weight of the thermoplastic elastomer composition.Aspect 146. The method of Aspect 144, wherein the foam article comprisesgreater than about 97 weight percent of the thermoplastic copolyesterbased on the total weight of the thermoplastic elastomer composition.Aspect 147. The method of Aspect 144, wherein the foam article comprisesgreater than about 98 weight percent of the thermoplastic copolyesterbased on the total weight of the thermoplastic elastomer composition.Aspect 148. The method of Aspect 144, wherein the foam article comprisesgreater than about 99 weight percent of the thermoplastic copolyesterbased on the total weight of the thermoplastic elastomer composition.Aspect 149. A foam article comprising a foamed polymeric materialcomprising the thermoplastic copolyester composition of any one ofAspects 1-53; wherein the foam article has a multicellular foamstructure.Aspect 150. The foam article of Aspect 149, wherein the foam article isan extruded foam article.Aspect 151. The foam article of Aspect 149, wherein the foam article isan injection molded foam article.Aspect 152. The foam article of Aspect 149, wherein the foam article isa compression molded foam article.Aspect 153. The foam article of any one of Aspects 149-152, wherein themulticellular foam structure has a closed cell foam microstructure.Aspect 154. The foam article of any one of Aspects 149-152, wherein themulticellular foam structure has an open cell foam microstructure.Aspect 155. The foam article of Aspect 154, wherein the multicellularfoam structure comprises less than 10 percent of cells having a closedcell microstructure.Aspect 156. The foam article of Aspect 154, wherein the multicellularfoam structure comprises less than 5 percent of cells having a closedcell microstructure.Aspect 157. The foam article of Aspect 154, wherein the multicellularfoam structure comprises less than 1 percent of cells having a closedcell microstructure.Aspect 158. The foam article of any one of Aspects 149-157, wherein themulticellular foam has an average cell size of from about 50 micron toabout 5 millimeters; from about 100 micron to about 1 millimeters; orfrom about 50 micron to about 1 millimeters.Aspect 159. The foam article of any one of Aspects 149-158, wherein thefoam article has a ply adhesion strength between the polymeric layer andthe foam component that is greater than 2.5 kg force/centimeter orgreater than 3.0 kg force/centimeter, when determined using the PlyAdhesion Test method described herein.Aspect 160. The foam article of any one of Aspects 149-159, wherein thefoam article has an average hand pull test result between the polymericlayer and the foam component that is greater than or equal to 2.0, orgreater than or equal to 2.5, or greater than or equal to 3.0, orgreater than or equal to 3.5, or greater than or equal to 4.0, orgreater than or equal to 4.5, when determined according to the Hand PullTest method described herein.Aspect 161. The foam article of any one of Aspects 149-160, wherein thelayer has an Akron abrasion of less than 0.50 cubic centimeters lost,optionally less than 0.40 cubic centimeters lost, less than 0.30 cubiccentimeters lost, less than 0.20 cubic centimeters lost, or less than0.10 cubic centimeters lost as determined using the Akron Abrasion Test.Aspect 162. The foam article of any one of Aspects 149-161, wherein thelayer has an Akron abrasion of less than 500 milligrams lost, optionallyless than 400 milligrams lost, less than 300 milligrams lost, less than200 milligrams lost, or less than 100 milligrams lost as determinedusing the Akron Abrasion Test.Aspect 163. The foam article of any one of Aspects 149-162, wherein thelayer has a DIN abrasion of less than 0.30 cubic centimeters lost,optionally less than 0.20 cubic centimeters lost, less than 0.10 cubiccentimeters lost, less than 0.05 cubic centimeters lost, or less than0.03 cubic centimeters lost as determined using the DIN Abrasion Test.Aspect 164. The foam article of any one of Aspects 149-163, wherein thelayer has a DIN abrasion of less than 300 milligrams lost, optionallyless than 250 milligrams lost, optionally less than 200 milligrams lost,optionally less than 150 milligrams lost, optionally less than 100milligrams lost, optionally less than 80 milligrams lost, optionallyless than 50 milligrams lost, or optionally less than 30 milligrams asdetermined using the DIN Abrasion Test.Aspect 165. The foam article of any one of Aspects 149-164, wherein thelayer has a dry dynamic coefficient of friction (COF) on a dry surfaceof greater than 0.5, optionally of greater than 0.7, greater than 0.8,greater than 0.9, greater than 1.0, as determined using the Dry OutsoleCoefficient of Friction Test.Aspect 166. The foam article of any one of Aspects 149-165, wherein thelayer has a wet dynamic COF of greater than 0.25, optionally of greaterthan 0.30, greater than 0.35, greater than 0.40, or greater than 0.50,as determined using the Wet Outsole Coefficient of Friction Test.Aspect 167. The foam article of any one of Aspects 149-166, wherein thefoam article has a maximum load of about 100 N to about 4000 N whendetermined using the Cyclic Tensile test as described herein.Aspect 168. The foam article of Aspect 167, wherein the foam article hasa maximum load of about 100 N to about 4000 N when determined using theCyclic Tensile test as described herein.Aspect 169. The foam article of any one of Aspects 149-168, wherein thefoam article has an energy efficiency of greater than or equal to about50 percent when determined using the Cyclic Compression test asdescribed herein.Aspect 170. The foam article of Aspect 169, wherein the foam article hasan energy efficiency of greater than or equal to about 60 percent whendetermined using the Cyclic Compression test as described herein.Aspect 171. The foam article of Aspect 169, wherein the foam article hasan energy efficiency of greater than or equal to about 70 percent whendetermined using the Cyclic Compression test as described herein.Aspect 172. The foam article of Aspect 169, wherein the foam article hasan energy efficiency of about 50 percent to about 97 percent whendetermined using the Cyclic Compression test as described herein.Aspect 173. The foam article of any one of Aspects 149-172, wherein thefoam article has an energy return of about 200 millijoules (mJ) to 1200mJ when determined using the Cyclic Compression test as describedherein.Aspect 174. The foam article of Aspect 173, wherein the foam article hasan energy return of about 400 mJ to 1000 mJ when determined using theCyclic Compression test as described herein.Aspect 175. The foam article of Aspect 173, wherein the foam article hasan energy return of about 600 mJ to 800 mJ when determined using theCyclic Compression test as described herein.Aspect 176. The foam article of any one of Aspects 149-175, wherein thefoam article has a split tear value of about 1.0 kilogram per centimeterto 4.5 kilogram per centimeter, about 1.6 kilogram per centimeter to 4.0kilogram per centimeter, about 2.0 kilogram per centimeter to 4.0kilogram per centimeter, about 2.0 kilogram per centimeter to 3.5kilogram per centimeter, about 2.5 kilogram per centimeter to 3.5kilogram per centimeter, about 0.07 kilogram per centimeter to 2.0kilogram per centimeter, or about 0.8 kilogram per centimeter to 1.5kilogram per centimeter, or about 0.9 to 1.2 kilogram per centimeter,about 1.5 kilogram per centimeter to 2.2 kilogram per centimeter; about0.08 kilogram per centimeter to 4.0 kilogram per centimeter, about 0.9kilogram per centimeter to 3.0 kilogram per centimeter, about 1.0 to 2.0kilogram per centimeter, about 1.0 kilogram per centimeter to 1.5kilogram per centimeter, or about 2 kilogram per centimeter using asplit tear test as described herein.Aspect 177. The foam article of any one of Aspects 149-176, wherein thefoam article has a split tear value of greater than or equal to about1.5 kg/cm, greater than or equal to about 2.0 kg/cm, or greater than orequal to about 2.5 kg/cm, when determined using a split tear test asdescribed herein.Aspect 178. The foam article of any one of Aspects 149-177, wherein thefoam article has a specific gravity of less than or equal to 0.9.Aspect 179. The foam article of Aspect 178, wherein the foam article hasa specific gravity of from about 0.02 to about 0.22; of from about 0.03to about 0.12; from about 0.04 to about 0.10; from about 0.11 to about0.12; from about 0.10 to about 0.12; from about 0.15 to about 0.2; 0.15to about 0.30; 0.01 to about 0.10; from about 0.02 to about 0.08; fromabout 0.03 to about 0.06; 0.08 to about 0.15; from about 0.10 to about0.12; from about 0.15 to about 0.2; from about 0.10 to about 0.12; fromabout 0.1 to about 0.35; from about 0.12 to about 0.20; from 0.02 toabout 0.22; from about 0.02 to about 0.20; from about 0.02 to about0.18; or from of about 0.02 to about 0.16.Aspect 180. The foam article of any one of Aspects 149-179, wherein thefoam article has a stiffness of about 200 kilopascals to about 1000kilopascals, for a cylindrical sample having a diameter of about 45millimeters as determined using the Cyclic Compression Test.Aspect 181. The foam article of Aspect 180, wherein the foam article hasa stiffness of about 400 kilopascals to about 900 kilopascals, for acylindrical sample having a diameter of about 45 millimeters asdetermined using the Cyclic Compression Test.Aspect 182. The foam article of any one of Aspects 149-181, wherein thefoam article has a change in displacement at max loading of about 1millimeters to about 5 millimeters when measured on foam slabs having athickness of about 1 centimeters, wherein the foam slabs are compressedfor about 5000 cycles of compression from 0 N to 300 N and back to 0 Nper cycle, using a 45 mm diameter cylindrical tupp as the compressionhead.Aspect 183. The foam article of any one of Aspects 149-182, wherein thefoam article has a change in displacement at max loading of about 2millimeters to about 4 millimeters when measured on foam slabs having athickness of about 1 centimeters, wherein the foam slabs are compressedfor about 5000 cycles of compression from 0 N to 300 N and back to 0 Nper cycle, using a 45 mm diameter cylindrical tupp as the compressionhead.Aspect 184. The foam article of any one of Aspects 149-183, wherein thefoam article comprises greater than about 90 weight percent of thethermoplastic copolyester based on the total weight of the thermoplasticelastomer composition.Aspect 185. The foam article of Aspect 184, wherein the foam articlecomprises greater than about 95 weight percent of the thermoplasticcopolyester based on the total weight of the thermoplastic elastomercomposition.Aspect 186. The foam article of Aspect 184, wherein the foam articlecomprises greater than about 97 weight percent of the thermoplasticcopolyester based on the total weight of the thermoplastic elastomercomposition.Aspect 187. The foam article of Aspect 184, wherein the foam articlecomprises greater than about 98 weight percent of the thermoplasticcopolyester based on the total weight of the thermoplastic elastomercomposition.Aspect 188. The foam article of Aspect 184, wherein the foam articlecomprises greater than about 99 weight percent of the thermoplasticcopolyester based on the total weight of the thermoplastic elastomercomposition.Aspect 189. An article comprising the foam article made by the method ofany one of Aspects 0-0, or the foam article of any one of Aspects149-188.Aspect 190. The article of any one of Aspects 189-234, wherein thearticle is an article of footwear.Aspect 191. The article of any one of Aspects 189-234, wherein the foamarticle is a cushioning element in the article of footwear.Aspect 192. The article of any one of Aspects 189-234, wherein thecushioning element is a component of a sole structure in the article offootwear.Aspect 193. The article of any one of Aspects 189-234, wherein the foamarticle is a component of a sole structure in the article of footwear.Aspect 194. The article of any one of Aspects 189-234, wherein the solestructure has a first side that is configured to be ground-facing whenthe sole structure is a component of an article of footwear, a secondside opposed to the first side, and a sidewall extending at leastpartially between the first side and the second side; wherein the layercomprising the second polymeric material is disposed on one or more ofthe first side, the second side, or the sidewall.Aspect 195. The article of any one of Aspects 189-234, wherein the solestructure is a midsole. Aspect 196. The article of any one of Aspects189-234, wherein the sole structure is a plate. Aspect 197. The articleof any one of Aspects 189-234, wherein the sole structure is a chassis.Aspect 198. The article of any one of Aspects 189-234, wherein the solestructure is a bladder.Aspect 199. The article of any one of Aspects 189-234, wherein the solestructure is a bladder, and the foam article is disposed on an exteriorsurface of the bladder.Aspect 200. The article of any one of Aspects 189-234, wherein the solestructure is a heel counter.Aspect 201. The article of any one of Aspects 189-234, wherein the solestructure comprises a shell component that at least partially enclosesthe foam article, wherein the shell component comprises the layercomprising the second polymeric material.Aspect 202. The article of any one of Aspects 189-234, wherein the shellcomponent encloses the foam article on the first side and the sidewallof the sole structure.Aspect 203. The article of any one of Aspects 189-234, wherein the shellcomponent is attached to the upper of the article of footwear.Aspect 204. The article of any one of Aspects 189-234, wherein the solestructure further comprises an outsole component on the ground-facingside of the sole structure.Aspect 205. The article of Aspect 204, wherein the outsole componentcomprises a thermoplastic elastomer (TPE) or thermoplastic vulcinazate(TPV).Aspect 206. The article of Aspect 205, wherein the thermoplasticvulcinazate is cross-linked.Aspect 207. The article of Aspect 205, wherein the thermoplasticvulcinazate is comprises a partially cross-linked rubber dispered into athermoplastic host phase.Aspect 208. The article of Aspect 207, wherein the partiallycross-linked rubber dispered into a thermoplastic host phase comprisesan ethylene propylene diene rubber in polypropylene (EPDM/PP), an alkylacrylic copolymer rubber in a polyamide host (ACM/PA), a silicone rubberdispersed in thermoplastic copolyester, or combinations thereof.Aspect 209. The article of any one of Aspects 189-208, wherein theoutsole component comprises a thermoplastic elastomer (TPE).Aspect 210. The article of Aspect 206, wherein the thermoplasticelastomer is selected from a copolyester, a thermoplastic polyurethane(TPU), a styrenic copolymer, an ethylenic copolymer, an ionomer, anacrylic copolymer elastomers, and combinations thereof.Aspect 211. The article of Aspect 207, wherein the styrenic copolymer isselected from a styrene butadiene rubber (SBR), a styrene ethylenebutadiene styrene (SEBS), a styrene ethylene propylene styrene (SEPS),and combinations thereof.Aspect 212. The article of Aspect 207, wherein the ethylenic copolymeris selected from an ethylene-propylene copolymer, an olefinic blockcopolymer, and combinations thereof.Aspect 213. The article of Aspect 207, wherein the olefinic blockcomprises poly(methyl methacrylate) blocks, acrylate blocks, poly(methylmethacrylate)-acrylate copolymeric blocks, and combinations thereof.Aspect 214. The article of any one of Aspects 204-213, wherein theoutsole component comprises a solid polymeric material that was formedwithout the addition of compressed gas, supercritical fluid or otherblowing agent.Aspect 215. The article of Aspect 214, wherein the outsole component hasa durometer less than Shore A 90, than Shore A 85, or less than Shore A80.Aspect 216. The article of Aspect 214, wherein the outsole component hasa durometer greater than Shore A 60 or Shore A 65.Aspect 217. The article of Aspect 214, wherein the outsole component hasa durometer less than Shore A 90, than Shore A 85, or less than Shore A80; and wherein the outsole component has a durometer greater than ShoreA 60 or Shore A 65.Aspect 218. The article of any one of Aspects 204-217, wherein theoutsole component comprises a thermoplastic elastomer (TPE) orthermoplastic vulcinazate (TPV); and wherein the outsole component has adensity less than about 1.25 grams per cubic centimeter, about 1.1 gramsper cubic centimeter, about 0.95 grams per cubic centimeter, or about0.9 grams per cubic centimeter.Aspect 219. The article of any one of Aspects 204-218, wherein theoutsole component comprises a ground contact layer, print-on outsole, orother exterior feature; wherein the ground contact layer, print-onoutsole, or other exterior feature is prepared using a fused deposition3D printing process; and wherein the fused deposition 3D printingprocess comprises using a preformed filament comprising a thermoplasticelastomer (TPE) or thermoplastic vulcinazate (TPV).Aspect 220. The article of Aspect 219, wherein the filament has adiameter of about 1.5 millimeters, 1.75 millimeters, 1.85 millimeters,2.85 millimeters, or 3.0 millimeters.Aspect 221. The article of Aspects 219 or 220, wherein the groundcontact layer, print-on outsole, or other exterior feature has adurometer less than Shore A 90, than Shore A 85, or less than Shore A80; and wherein the outsole component has a durometer greater than ShoreA 60 or Shore A 65.Aspect 222. The article of any one of Aspects 219-221, wherein theground contact layer, print-on outsole, or other exterior feature has adensity less than about 1.25 grams per cubic centimeter, about 1.1 gramsper cubic centimeter, about 0.95 grams per cubic centimeter, or about0.9 grams per cubic centimeter.Aspect 223. The article of any one of Aspects 204-222, wherein theoutsole component is injected molded.Aspect 224. The article of Aspect 223, wherein the injection moldingcomprises the use of a compressed gas, a supercritical fluid, or acombination thereof.Aspect 225. The article of Aspect 223, wherein the injection moldingcomprises the use of a chemical foaming agent.Aspect 226. The article of Aspect 223, wherein the injection moldingcomprises the use of a compressed gas, a supercritical fluid, a chemicalfoaming agent, or a combination thereof.Aspect 227. The article of any one of Aspects 189-234, wherein theoutsole component exhibits a dry traction coefficient of friction ofabout 0.9, of about 1.0, or about 1.1 by methods as defined herein.Aspect 228. The article of any one of Aspects 189-234, wherein theoutsole component exhibits a wet traction coefficient of friction ofabout 0.3, about 0.4, or about 0.5 by methods as defined herein.Aspect 229. The article of any one of Aspects 189-234, wherein theoutsole component comprising TPE or TPV polymers exhibits abrasionresistance as defined per the DIN or rotary drum abrasion test of lessthan 250 milligrams lost per test, optionally less than 200 milligramslost per test, and preferably less than 150 milligrams lost per test, orless than 100 milligrams lost per test, or less than 80 milligrams lostper test by methods as defined herein.Aspect 230. The article of any one of Aspects 189-234, wherein theoutsole component comprises a cured rubber.Aspect 231. The article of any one of Aspects 189-234, wherein theoutsole has a density of less than or equal to about 0.90 grams percubic centimeter.Aspect 232. The article of any one of Aspects 189-234, wherein theoutsole has a density of less than or equal to about 0.85 grams percubic centimeter.Aspect 233. The article of any one of Aspects 189-234, wherein theoutsole has a density of less than or equal to about 0.50 grams percubic centimeter.Aspect 234. The article of any one of Aspects 189-234, wherein theoutsole has a density about 0.60 grams per cubic centimeter to about0.90 grams per cubic centimeter.Aspect 235. The article of any one of Aspects 189-234, wherein theoutsole has a density about 0.60 grams per cubic centimeter to about0.85 grams per cubic centimeter.Aspect 236. The article of any one of Aspects 189-234, wherein theoutsole has a density about 0.60 grams per cubic centimeter to about0.80 grams per cubic centimeter.Aspect 237. The article of any one of Aspects 189-234, wherein a side ofthe foam article is bonded to an upper.Aspect 238. The article of any one of Aspects 189-234, wherein the uppercomprises a polyester yarn, a polyester fiber, a thermoplasticpolyurethane yarn, a thermoplastic polyurethane fiber, or combinationsthereof.Aspect 239. The article of any one of Aspects 189-234, wherein the sideof the foam article bonded to an upper is bonded using an adhesive.Aspect 240. The article of any one of Aspects 189-234, wherein the sideof the foam article bonded to an upper is essentially free of anadhesive at a bond interface between the side of the foam article andthe upper.Aspect 241. The article of any one of Aspects 189-234, wherein the solestructure further comprises an outsole component on a ground-facing sideof the outsole component.Aspect 242. The article of any one of Aspects 189-234, wherein theoutsole component comprises a cured rubber.Aspect 243. The article of any one of Aspects 189-234, wherein thearticle comprises a side of the foam article bonded to an upper.Aspect 244. The article of any one of Aspects 189-234, wherein the uppercomprises a thermoplastic polyester yarn, a thermoplastic polyesterfiber, a thermoplastic polyurethane yarn, a thermoplastic polyurethanefiber, a thermoplastic polyamide yarn, a thermoplastic polyamide fiber,or combinations thereof.Aspect 245. The article of any one of Aspects 189-234, wherein the sideof the foam article bonded to an upper is bonded using an adhesive.Aspect 246. The article of any one of Aspects 189-234, wherein the sideof the foam article bonded to an upper and is essentially free of anadhesive at a bond interface between the side of the foam article andthe upper.Aspect 247. The article of any one of Aspects 189-234, wherein thearticle is an article of apparel.Aspect 248. The article of any one of Aspects 189-234, wherein thearticle is an article of sporting equipment.Aspect 249. A method for manufacturing an article of footwear, themethod comprising:affixing a foam article and a textile element to each other;wherein the foam article is a form article of any one of Aspects 54-148;orwherein the foam article is a form article is made by the method one ofAspects 149-188.Aspect 250. A method for manufacturing an article of footwear, themethod comprising:affixing an outsole to the midsole to a midsole;wherein the outsole comprises an outsole thermoplastic copolyester; andwherein the midsole comprises a form article of any one of Aspects54-148, or a form article is made by the method one of Aspects 149-188.Aspect 251. The method of Aspect 236, wherein the outsole thermoplasticcopolyester comprises a thermoplastic copolyester of any one of Aspects1-53.Aspect 252. The method of Aspect 236, wherein the outsole thermoplasticcopolyester is substantially free of a thermoplastic copolyester of anyone of Aspects 1-53.Aspect 253. The method of any one of Aspects 236-238, wherein outsole issubstantially free of a foamed outsole thermoplastic copolyester.Aspect 254. The method of any one of Aspects 236-238, wherein outsolecomprises a foamed outsole thermoplastic copolyester.Aspect 255. The method of any one of Aspects 236-240, wherein themidsole comprises a midsole foamed thermoplastic copolyester compositioncomprising a first polymeric component including at least one firstthermoplastic copolyester, and the outsole comprises an outsolethermoplastic copolyester composition comprising a second polymericcomponent including at least one second thermoplastic copolyester, andwherein a concentration of an additive in the foamed thermoplasticcopolyester composition differs from a concentration of the additive inthe outsole thermoplastic copolyester composition by at least 10 weightpercent, or a first concentration of the first polymeric component inthe foamed thermoplastic copolyester composition differs from a secondconcentration of the second polymeric component in the outsolethermoplastic copolyester composition by at least 10 weight percent, ora chemical structure of the first at least one thermoplastic copolyesterdiffers from a chemical structure of the second at least onethermoplastic copolyester, or a number average molecular weight of thefirst at least one thermoplastic copolyester differs from a numberaverage molecular weight of the second at least one thermoplasticcopolyester by at least 10 percent, or any combination thereof.Aspect 256. The method of any one of Aspects 236-241, wherein theaffixing comprises injection molding an outsole, and then injectionmolding the midsole directly onto the outsole.Aspect 257. The method of any one of Aspects 236-241, wherein theaffixing comprises thermally bonding the midsole to the outsole.Aspect 258. A molding system for forming a foam article, the systemcomprising:a barrel housing a screw configured to receive a molten polymericmaterial and form a mixture of the molten polymeric material comprisinga thermoplastic elastomer and a blowing agent, and toadjust a position of the screw in the barrel to regulate a flowrate ofthe mixture out of the barrel;a mold cavity configured to contain the mixture during foaming, mold thefoamed mixture, and solidify the molded foamed mixture into the foamarticle;an injection or extrusion device configured to receive the mixture andextrude or inject it into the mold cavity at an injection pressure andtemperature; anda temperature control and monitoring system configured to control theinjection temperature or a foaming temperature at which the moltenpolymeric material is foamed within the mold cavity, or both.Aspect 259. The molding system of Aspect 244, wherein the temperaturecontrol and monitoring system is configured to control the injectiontemperature of the mixture or the foaming temperature of the moltenpolymeric material or both within a temperature ranging from about themelting temperature of the thermoplastic elastomer to about 50 degreesC. above the tail temperature of the thermoplastic elastomer.Aspect 260. The molding system of Aspect 244 or 245, further comprisinga gas counter pressure assembly coupled to the mold cavity, wherein thegas counter pressure assembly is configured to regulate an amount ofcounter pressure gas flow into the mold cavity before, during or afterextruding or injecting the mixture into the mold cavity, or duringfoaming of the molten polymeric material in the mold cavity.Aspect 261. The molding system of any one of Aspects 244-246, furthercomprising a mold cavity venting system configured to regulate a rate ofpressure loss due to gas flow out of the mold cavity.Aspect 262. The molding system of any one of Aspects 244-247, whereinthe system further comprises a runner system in fluid communication withthe injection or extrusion device and the mold cavity.Aspect 263. The molding system of Aspect 248, wherein the runner systemis configured to control a temperature of the mixture as it flowsthrough the runner.Aspect 264. The molding system of Aspect 249, wherein the runner systemis configured to heat the mixture as it flows through the runner.Aspect 265. The molding system of any one of Aspects 244-250, whereinthe system includes a pressure control assembly configured to control apressure of the mixture as it enters the mold cavity.Aspect 266. A method for operation of a molding system for forming afoam article, the method comprising:forming a mixture of a molten polymeric material comprising athermoplastic elastomer and a blowing agent in a barrel housing a screw;adjusting a position of the screw in the barrel to regulate a flowrateof the mixture out of the barrel;

-   -   flowing the mixture from the barrel into a mold cavity;        extruding or injecting the mixture into the mold cavity at an        injection pressure and an injection pressure;        foaming the molten polymeric material in the mold cavity at a        foaming temperature, thereby forming a foamed molten polymeric        material; and        solidifying the foamed molten polymeric material in the mold        cavity, thereby forming a foam article having a multicellular        foam structure.        Aspect 267. The method of operation of Aspect 252, wherein the        method further comprises monitoring and controlling the        injection temperature of the mixture or the foaming temperature        of the molten polymeric material or both within a temperature        ranging from about the melting temperature of the thermoplastic        elastomer to about 50 degrees C. above the tail temperature of        the thermoplastic elastomer.        Aspect 268. The method of operation of Aspect 252 or 253,        further comprising regulating an amount of counter pressure gas        flowing into the mold cavity before, during or after extruding        or injecting the mixture into the mold cavity, or during foaming        of the molten polymeric material in the mold cavity.        Aspect 269. The method of operation of Aspect 252-254, further        comprising releasing gas from the mold cavity at a controlled        rate during the extruding or injecting or during the foaming.        Aspect 270. The method of operation of Aspect 252-255, further        comprising controlling a temperature of the mixture as it flows        through a runner into the mold cavity.        Aspect 271. The method of operation of Aspect 252-256, further        controlling the injection pressure of the mixture as it enters        the mold cavity.        Aspect 272. The method of operation of Aspect 252-257, wherein        the molten polymeric material comprises a thermoplastic        copolyester according any one of Aspects 1-53, or the method is        a method of making a foam article according to any one of        Aspects 54-148, or the foam article comprises a foam article        according to any one of Aspects 149-188, or any combination        thereof.

Examples

Now having described the aspects of the present disclosure, in general,the following Examples describe some additional aspects of the presentdisclosure. While aspects of the present disclosure are described inconnection with the following examples and the corresponding text andfigures, there is no intent to limit aspects of the present disclosureto this description. On the contrary, the intent is to cover allalternatives, modifications, and equivalents included within the spiritand scope of the present disclosure.

Materials.

HYTREL 3078 and HYTREL 4068 were obtained from DuPont (Wilmington, Del.,USA).

Processing Conditions.

Foam plaques were prepared according to the conditions shown in Table 1below:

TABLE 1 Melt Mold Injection Fill Temp Temp Speed time MPP N₂ GCP GCPMaterial (° C.) (° C.) (cc/sec) (s) (Bar) (%) (PSI) release Hytrel 21054 100 2.5 175 0.5 600 End of 4068 fill Hytrel 200 40 100 2.5 175 0.5600 End of 3078 fill

Foam midsoles were prepared according to the conditions shown in Table 2below:

TABLE 2 Injec- Cool- Melt Mold tion Fill ing GCP Ma- Temp Temp Speedtime Time MPP N2 GCP re- terial (° C.) (° C.) (cc/sec) (s) (s) (Bar) (%)(PSI) lease Hytrel 210 54 100 2.5 400 175 1.22 600 End 4058 of fillHyteil 200 40 100 2.5 400 175 1.5 500 End 3078 of fill

Foam plaques were prepared according to the conditions shown in Table 3below.

TABLE 3 Mold Temperature Mold relative to Temperature Mold peak relativeto tail Temperature temperature temperature Foam No. Polyester (degreesC.) (degrees C.) (degrees C.) Quality 1 Triel ® 5400 160 +5 −16 Good 2Toyobo P- 175 0 −18 Poor 30B 3 Toyobo P- 190 +15 −3 Good 30B 4 Toyobo P-205 +30 +12 Coarse 30B 5 Toyobo P- 245 +70 +52 Coarser 30B

Cross-sectional views of the foam plaques described above are shown inFIGS. 9A-9D (for Nos. 2-5 above) and FIG. 10 (for No. 1 above).

Example 1. Exemplary Data of Foam Plaques

Foam plaques were prepared as described above using HYTREL 4068.Exemplary compression data are shown in FIG. 6. The data were obtainedby a cyclic compression testing protocol on a plaque in the form of acylindrical tupp having the following dimensions: thickness—20 mm;diameter—44.86 mm. The compression data in FIG. 6 are a representativecompression curve. The data obtained from these tests are summarized inTable 4 below.

TABLE 4 Average Average Energy Modulus Stiffness Max Efficiency ReturnMaterial (kPa) (N/mm) Strain (%) (mJ) Hytrel 4068 554 80 0.377 87 397

The specific gravity for foam plaques, prepared as described hereinabove, was determined to be 0.16-0.28 for HYTREL 4068 and 0.17-0.26HYTREL 3078.

The foam plaques described in Table 3 above were subjected to energyreturn analysis as described herein. The results are shown in Table 5below.

TABLE 5 Energy Return No. Polyester (mJ) 1 Triel ® 5400 2830 2 Toyobo P-2050 30B 3 Toyobo P- 2940 30B 4 Toyobo P- 3150 30B 5 Toyobo P- 2950 30B

Example 2. Exemplary Data of Foam Midsoles

Foam midsoles were prepared as described above using HYTREL 4068.Compression data were obtained by a cyclic compression testing protocolusing a footform as described above. The data obtained from these testsare summarized in Table 6 below.

TABLE 6 Average Average Max Energy Modulus Stiffness DisplacementEfficiency Return Material (kPa) (N/mm) Strain (%) (mJ) Hytrel 4068 N/A173 11.57 74 4078

The specific gravity for foam midsoles, prepared as described hereinabove, was determined to be 0.19-0.27 for HYTREL 4068 and 0.19-0.26HYTREL 3078.

Example 3. Exemplary Hand Pull Data

A foam article was prepared comprising a first foam component and asecond s component. The first foam component was an open-cell foamformed from a first thermoplastic copolyester composition comprisingHYTREL 4068 which contained less than 1 weight percent of non-polymericmaterials. The first thermoplastic copolyester composition was injectionmolded, foamed and bonded in place to the second solid component. Thethermoplastic copolyester composition was foamed using the MUCELLprocess by forming a single-phase solution of carbon dioxide and thethermoplastic copolyester composition. The first thermoplasticcopolyester composition was injection molded and foamed onto a preformedsecond component as described herein below. The second solid componentwas prepared as a solid plaque using a second thermoplastic copolyestercomposition, i.e., a second polymeric material comprising one of thefour listed copolyesters shown in the table below (MP IN15074, HYTREL3078, TRIEL 5202SU, and SP9339, which are further described in Table 8).The first foam component was bonded to the second foam component, i.e.,a plaque comprising a solid second polymeric material, by injecting,foaming, and molding a single-phase solution of carbond dioxide and athermoplastic copolyester composition comprising HYTREL 4068 onto theoutsole plaque in an injection mold. Prior to placing the outsole plaqueinto the mold, one of the following treatments was used: a) no surfacepreparation was conducted on the surface of the outsole plaque ontowhich the foam was injected (i.e., control sample); b) the outsoleplaque surface was wiped with methyl ethyl ketone prior to insertioninto the mold; c) the outsole plaque surface was treated using arotating cone open air plasma treatment immediately prior to insertioninto the mold and injection of the foam composition, where the plaquesurface was held 1 cm away from the emitting head, and the plaque wasmoved passed the emitting head at a rate of about 100-200 mm/sec; or d)the outsole plaque was heated using an infrared lamp for at least 30seconds immediately prior to insertion into the mold and injection ofthe foam composition. The equipment used was a PlasmatreatOPENAIR-PLASMA System with an RD1004 head (Plasmatreat GmbH, Steinhagen,Germany).

Hand pull data were obtained using the Hand Pull Test as describedherein above. The data obtained are shown in Table 7 below. The data inTable 7 indicate that good bonding of the foam to an outsole materialcan be achieved using a direct bonding process with little if anyadditional process steps prior to foaming and molding in place the firstfoam component.

TABLE 7 Surface Prep of Outsole Polymer* Foam Plaque MP IN15074 HY3078TRIEL 5202SU SP9339 No treatment 1 2 3.5 2 MEK wipe 1 3 3 3 Plasmatreat1.5 4.5 4 3.5 IR pre-treatment 1 4.5 4 4 *Values correspond to thefollowing results in Hand Pull Test: 1—easy to peel adhesive failure;2—adhesive failure, but some resistance; 3—4.5 cohesive foam failure,varying levels of foam skin failure; and 5—unable separate)

Example 4. Exemplary Data of Second Polymeric MaterialCharacterization—Coefficient of Friction—Polymer Samples

Sample preparation, coefficient of friction, and other test procedureswere carried out as described herein above. The coefficient of frictiondata for wood and concrete surfaces are shown in the table shown inFIGS. 11 and 12, respectively. The materials referred into FIGS. 11 and12 are further described in Table 8 below.

TABLE 8 Material Grade Polymer type Form Supplier Apilon 52 TPU SolidAPI Plastics BT 1030D CoPe TPE Solid LG Desmopan 8795A TPU Foam CovestroEllastolan b70a TPU Solid Lubrizol Ellastolan SP9339 TPU Foam BASFEllastolan SP9500 TPU Solid BASF Estane 2350-75a-030 TPU Solid LubrizolEstane 58238 TPU Solid Lubrizol Estane t470a-3 TPU Solid Lubrizol HPFAD1035 Ethlyenic TPE/ Solid DuPont Ionomer HPF AD1172 Ethlyenic TPE/Solid DuPont Ionomer Hytrel 3078 CoPe TPE Solid DuPont Hytrel 3078 CoPeTPE Foam DuPont Hytrel 3078 CoPe TPE Solid DuPont Hytrel 4068 CoPe TPEFoam DuPont Hytrel 4556 CoPe TPE Solid DuPont KP3340 CoPe TPE SolidKolon KP3347 CoPe TPE Solid Kolon Kurarity LA2250 Acrylic TPE SolidKuraray Kurarity LA4285 Acrylic TPE Solid Kuraray Monprene 12990 SEBSTPE Foam Teknor Apex Monprene 66070 SEBS TPE Solid Teknor Apex MonpreneCP28160-01 SEBS TPE Solid Teknor Apex Monprene IN15056 SEBS TPE SolidTeknor Apex Monprene IN15074 SEBS TPE Solid Teknor Apex Monprene IN15074SEBS TPE Foam Teknor Apex Monprene SP16074H SEBS TPE Solid Teknor ApexMonprene SP16975 SEBS TPE Solid Teknor Apex Santoprene 123-40 TPV:EPDM/PP Solid - Exxon Herringbone Santoprene 201-64 TPV: EPDM/PP Solid -Exxon Herringbone Santoprene 103-50 TPV: EPDM/PP Solid - ExxonHerringbone Sarlink 3160 TPV: EPDM/PP Solid Teknor Apex Sarlink 6755BTPV: EPDM/PP Solid Teknor Apex Sarlink 6755N TPV: EPDM/PP Solid TeknorApex Septon blends w/PP SEBS/ Solid Kuraray (16-011-4) PP compoundSepton blends w/PP SEBS/ Solid Kuraray (16-051-1) PP compound Septonblends w/PP SEBS/ Solid Kuraray (16-078-2) PP compound Surlyn 8150Ethlyenic TPE/ Solid DuPont Ionomer Surlyn 8320 Ethlyenic TPE/ SolidDuPont Ionomer Surlyn 9320 Ethlyenic TPE/ Solid DuPont Ionomer TopgreenRH 1502-2 CoPe TPE Solid FENC Topgreen RH 1601-7 CoPe TPE Solid FENCTPSiV-50A TPV: Silicone/ Solid DuPont Hytrel TPSiV-60A TPV: Silicone/Solid DuPont Hytrel Triel 5202SP CoPe TPE Solid SamYang Triel 5202SPCoPe TPE Foam SamYang Triel 5300 CoPe TPE Solid SamYang Triel 5401A TPUSolid SamYang Triel SY 5280 CoPe TPE Solid SamYang Tuftec P1500 SEBS TPESolid Asahi Tuftec P5051 SEBS TPE Solid Asahi Zeotherm 100-70B TPV:ACM/PA Solid Zeon Chemical Zeotherm 100-80B TPV: ACM/PA Solid ZeonChemical Zeotherm 110-70B TPV: ACM/PA Solid Zeon Chemical Zeotherm130-90B TPV: ACM/PA Solid Zeon Chemical

Table 8, the abbreviations used therein have the following meaning:“TPU” means “Thermoplastic Polyurethane”; CoPe TPE means “CopolyesterThermoplastic Elastomer”; “Ethylenic TPE/Ionomer” means “EthylenicThermoplastic Elastomer/Ionomer”; “Acrylic TPE” means “AcrylicThermoplastic Elastomer”; “SEBS TPE” means“Styrene-Ethylene-Budiadiene-Styrene Thermoplastic Elastomer”;“TPV/EPDM/PP” means “Styrene-Ethylene-Budiadiene-Styrene ThermoplasticElastomer Thermoplastic Vulcanizate of Ethylene Propylene Diene MonomerRubber and Thermoplastic Polypropylene”; “TPV: Silicone/Hytrel” means“Thermoplastic Vulcanizate of Silicone Rubber and ThermoplasticCopolyester”; and “TPV: ACM/PA” means “Thermoplastic Vulcanizate ofAcryl Acrylate Copolymer Rubber and Thermoplastic Polyamide”.

Example 5. Exemplary Data of Second Polymeric MaterialCharacterization—Coefficient of Friction—Blown Outsole Samples

Sample preparation, coefficient of friction, and other test procedureswere carried out as described herein above. The coefficient of frictiondata for concrete surfaces are shown in the table shown in FIG. 13. Thematerials referred into FIG. 13 are further described in Table 8 above.

Example 6. Exemplary Data of Second Polymeric MaterialCharacterization—Specific Gravity—Blown Outsole Samples

Sample preparation and specific gravity test procedures were carried outas described herein above. The coefficient of friction data for concretesurfaces are shown in the table shown in FIG. 14. The samplesapproximated ‘blown’ rubber via physically foamed thermoplastic resinsusing added compressed gas or SCF. The materials referred into FIG. 14are further described in Table 8 above.

Example 7. Exemplary Data for High Aspect Ratio Injection Cavity Mold

FIGS. 16A-16F compare foam microstructures between injected parts of thesame overall shape but having different gate configurations such as afour-gate configuration as shown in FIG. 15A or as a six-gateconfiguration as shown in FIG. 15B. The different regions created by thefour-gate versus six-gate configuration is shown in the images shown inFIGS. 16G and 16H, respectively. Each part was composed of the samematerial, has equivalent density, and was injected under the sameconditions. As shown, FIGS. 16A-16C show photographic images of foamcross-sections obtained from the regions identified respectively as A,B, and C in the image for a component injection molded with thefour-gate configuration shown in FIG. 16G. and FIGS. 16D-16F showphotographic images of foam cross-sections obtained from the regionsidentified respectively as D, E, and F in the image for a componentinjection molded with the four-gate configuration shown in FIG. 16H.FIG. 16I shows a representative defect free foam microstructurecharacteristic of either gating scenario. The images shown aconsiderable decrease in largest defect size and overall defect area fora part obtained using a six-gate configuration compared to a part ofoverall equivalent size, but molded using a four-gate configuration.Notably, there are marked differences in largest defect size (δ) (wherea defect is defined as any area with a single dimension >1 mm, indicatedwith red dots) and overall defect area (Δ) between the image pairs whenthe AR is different. In all cases, the images corresponding to higheraspect ratio injection cavities have smaller defects and lower totaldefect area compared to the lower aspect ratio cavities. In areas absentof defects, the foam cells themselves have similar structure (I)regardless of gate configuration. Table 9 summarizes the aspect ratio(AR), maximum area for an individual defect (δ), and total defect area(Δ) for each image.

TABLE 9 AR δ [mm²] Δ [mm²] A 2.8 30 40 D 3.9 1.2  2 B 2.7 85 90 E 7.51.7 10 C 5.2 1.7 10 F 5.2 2 10

For the foregoing calculations, the following definitions apply: (1)Volume for each gate—from the gate volume, the center of mass wascalculated, and from the center of mass, the shortest distance to thesurface of the gate's volume (L_(min)) and the longest distance to thesurface of the gate's volume (L_(max)) were identified; (2) Aspect Ratiois (L_(max))/(L_(min)); and (3) Defect Measurement—a defect was definedas an area in a micrograph where a 1 mm line could be drawn withoutcrossing a foam strut is defined as a defect and regions correspondingto defects are indicated with the indicated dots in FIGS. 16A-16F. Thearea of each defect was calculated by fitting a polygon consisting of anarbitrary number of edges to each area of interest. In Table 9, thedefect with the largest area is given by δ and the sum of all the defectarea is given by Δ.

It should be emphasized that the above-described aspects of the presentdisclosure are merely possible examples of implementations, and are setforth only for a clear understanding of the principles of thedisclosure. Many variations and modifications may be made to theabove-described aspects of the disclosure without departingsubstantially from the spirit and principles of the disclosure. All suchmodifications and variations are intended to be included herein withinthe scope of this disclosure.

What is claimed:
 1. A method for making a foam midsole for an article offootwear, the method comprising: forming a mixture of a moltenthermoplastic copolyester composition comprising at least onethermoplastic copolyester elastomer and a physical blowing agent;injecting the mixture into a mold cavity; foaming the moltenthermoplastic copolyester composition in the mold cavity, therebyforming a foamed molten thermoplastic copolyester composition;solidifying the foamed molten thermoplastic copolyester composition,thereby forming a molded foam midsole having an open cell foam structureand compositionally comprising a thermoplastic copolyester composition;and removing the molded foam midsole from the mold cavity; wherein thethermoplastic copolyester composition comprises a thermoplasticcopolyester elastomer including (a) a plurality of first segments, eachfirst segment derived from a dihydroxy-terminated polydiol; (b) aplurality of second segments, each second segment derived from a diol;and (c) a plurality of third segments, each third segment derived froman aromatic dicarboxylic acid.
 2. The method of claim 1, wherein the atleast one thermoplastic copolyester elastomer comprises (a) a pluralityof first copolyester units, each first copolyester unit of the pluralitycomprising the first segment derived from a dihydroxy-terminatedpolydiol and the third segment derived from an aromatic dicarboxylicacid, wherein the first copolyester unit has a structure represented bya formula 1:

wherein R₁ is a group remaining after removal of terminal hydroxylgroups from the poly(alkylene oxide) diol of the first segment, whereinthe poly(alkylene oxide) diol of the first segment is a poly(alkyleneoxide) diol having a number-average molecular weight of about 400 toabout 6000; and wherein R₂ is a group remaining after removal ofcarboxyl groups from the aromatic dicarboxylic acid of the thirdsegment; and (b) a plurality of second copolyester units, each secondcopolyester unit of the plurality comprising the second segment derivedfrom a diol and the third segment derived from an aromatic dicarboxylicacid, wherein the second copolyester unit has a structure represented bya formula 2:

wherein R₃ is a group remaining after removal of hydroxyl groups fromthe diol of the second segment derived from a diol, wherein the diol isa diol having a molecular weight of less than about 250; and wherein R₂is the group remaining after removal of carboxyl groups from thearomatic dicarboxylic acid of the third segment.
 3. The method of claim2, wherein the first copolyester unit has a structure represented by aformula 3:

wherein R is H or methyl; wherein y is an integer having a value from 1to 10; wherein z is an integer having a value from 2 to 60; and whereina weight average molecular weight of each of the plurality of firstcopolyester units is from about 300 Daltons to about 7,000 Daltons. 4.The method of claim 3, wherein y is an integer having a value of 1, 2,3, 4, or
 5. 5. The method of claim 3, wherein R is hydrogen; wherein Ris methyl; wherein R is hydrogen and y is an integer having a value of1, 2, or 3; or wherein R is methyl and y is an integer having a valueof
 1. 6. The method of claim 2, wherein the first copolyester unit has astructure represented by a formula 4:

wherein z is an integer having a value from 2 to 60; and wherein aweight average molecular weight of each of the plurality of firstcopolyester units is from about 300 Daltons to about 7,000 Daltons. 7.The method of claim 6, wherein z is an integer having a value from 5 to60; from 5 to 50; from 5 to 40; from 4 to 30; from 4 to 20; or from 2 to10.
 8. The method of claim 1, wherein the thermoplastic copolyestercomposition consists essentially of the at least one thermoplasticcopolyester elastomer.
 9. The method of claim 1, wherein thethermoplastic copolyester composition further comprises an additive, andwherein the additive is a wax, an anti-oxidant, a UV-absorbing agent, acoloring agent, or any combination thereof.
 10. The method of claim 9,wherein the additive is present in an amount from about 0.1 weightpercent to about 4 weight percent based on the total weight of thethermoplastic copolyester composition.
 11. The method of claim 9,wherein the thermoplastic copolyester composition consists essentiallyof the at least one thermoplastic copolyester elastomer and theadditive.
 12. The method of claim 1, wherein the thermoplasticcopolyester composition further comprises an inorganic filler.
 13. Themethod of claim 12, wherein the inorganic filler is present in an amountfor from about 0.1 weight percent to about 4 weight percent based on thetotal weight of the thermoplastic copolyester composition.
 14. Themethod of claim 1, wherein the physical blowing agent is supercriticalnitrogen or supercritical carbon dioxide.
 15. The method of claim 14,wherein the supercritical nitrogen or supercritical carbon dioxide ispresent in the mixture in an amount of about 1% to about 5% by weightbased on upon a total weight of the mixture.
 16. The method of claim 1,wherein the at least one thermoplastic copolyester elastomer does notform crosslinks during the foaming or during the solidifying.
 17. Themethod of claim 1, wherein the injecting the mixture into the moldcavity comprises injecting the mixture into a pressurized mold cavityhaving a first pressure greater than atmospheric pressure.
 18. Themethod of claim 1, wherein the mixture has an injection temperature; andwherein the injection temperature is at least 20 degrees C. above thetail temperature of the at least one thermoplastic copolyesterelastomer.
 19. The method of claim 1, wherein the foaming occurs at afoaming temperature; and wherein the foaming temperature is at least 20degrees C. above the tail temperature of at least one thermoplasticcopolyester elastomer.
 20. The method of claim 1, wherein the foamingcomprises releasing pressure from the mold cavity at a mold cavitypressure release rate, and the mold cavity pressure release rate isabout 10 psi per sec to about 600 psi per sec.